Water-soluble phthalocyanine compound-containing ink for ink jetting, ink jet recording method and method for improving ozone gas discoloration of colored image material

ABSTRACT

To provide an ink capable of giving an image having excellent (color) hue and high fastness to light and ozone gas, an ink for ink jetting containing the ink, an ink jet recording method, and a method for enhancing the ozone resistance of an image. An ink comprising a water-soluble phthalocyanine compound, wherein in the spectral absorption curve of an aqueous solution of the phthalocyanine compound, the absorbance ratio b/a of the maximum absorbance b in the absorption band of 660 to 680 nm and the maximum absorbance a in the absorption band of 600 to 640 nm is less than 0.8 and the counter ion for the ionic hydrophilic group of the phthalocyanine compound is lithium ion.

TECHNICAL FIELD

The present invention relates to a coloring composition containing amedium and a phthalocyanine compound, more specifically, the presentinvention relates to an ink, a coating material, particularly cyan colorink, an ink for ink jet recording, an ink jet recording method and amethod for improving ozone gas discoloration resistance of an imagerecorded material obtained by ink jet recording.

BACKGROUND ART

In recent years, the image recording material is predominatedparticularly by a material for forming a color image. More specifically,a recording material using an ink jet system, a recording material usinga heat-sensitive transfer system, a recording material using anelectro-photographic system, a silver halide light-sensitive materialusing a transfer system, a printing ink, a recording pen and the likeare popularly used. Also, a color filter for recording/reproducing acolor image is used in an image pick-up element such as CCD ofphotographing equipment, or in LCD or PDP of display. In these colorimage recording materials or color filters, three primary color dyes(dyes or pigments) by a so-called additive or subtractive color mixingmethod are used for reproducing or recording a full color image,however, a dye having absorption properties capable of realizing apreferred color reproduction region and having fastness capable ofenduring various use and environmental conditions is not found atpresent and improvements are keenly demanded.

The ink jet recording method has been abruptly spread and is furthergrowing because the material cost is low, high-speed recording can beobtained, noises are less generated at the recording and color recordingis easy. The ink jet recording method includes a continuous system ofcontinuously jetting out a liquid droplet and an on-demand system ofjetting out a liquid droplet according to image information signals, andthe ejection system therefor includes a system of ejecting a liquiddroplet by generating bubbles in ink using heat, a system of using anultrasonic wave, and a system of ejecting a liquid droplet by suctionusing an electrostatic force. The ink used for ink jetting includes anaqueous ink, an oily ink and a solid (fusion-type) ink.

The dye used in the ink for ink jetting is required to have goodsolubility or dispersibility in a solvent, enable high-densityrecording, provide good (color) hue, have fastness to light, heat andactive gas in environment (for example, oxidative gas such as NOx andozone, and SOx), exhibit excellent resistance against water andchemicals, ensure good fixing property to an image-receiving material tocause less blurring, give an ink having excellent storability, have notoxicity and high purity and be available at a low cost.

In particular, the dye is strongly demanded to have good cyan color andfastness to light, humidity and heat and when printed on animage-receiving material having an ink-accepting layer containing aporous white inorganic pigment particle, be resistant against oxidativegas such as ozone in the environment.

A representative skeleton of the cyan dye used for ink is aphthalocyanine or triphenylmethane structure. Representative examples ofthe phthalocyanine compound which has been reported and is used over thewidest range include phthalocyanine derivatives classified into thefollowing (1) to (6):

-   (1) copper phthalocyanine compounds such as Direct Blue 86 and    Direct blue 87 [for example, Cu-Pc-(SO₃Na)_(m): a mixture of m=1 to    4] (hereinafter, Pc means a phthalocyanine skeleton);-   (2) Direct Blue 199 and phthalocyanine dyes described in    JP-A-62-190273 (the term “JP-A” as used herein means an “unexamined    published Japanese patent application”), JP-A-63-28690,    JP-A-63-306075, JP-A-63-306076, JP-A-2-131983, JP-A-3-122171,    JP-A-3-200883, JP-A-7-138511, etc. [for example,    Cu-Pc-(SO₃Na)_(m)(SO₂NH₂)_(n): a mixture of m+n=1 to 4];-   (3) phthalocyanine-base dyes described in JP-A-63-210175,    JP-A-63-37176, JP-A-63-304071, JP-A-5-171085, WO00/08102, etc. [for    example,. CU-Pc-(CO₂H)_(m)(CONR₁R₂)_(n): a mixture of m+n=0 to 4];-   (4) phthalocyanine-base dyes described in JP-A-59-30874,    JP-A-1-126381, JP-A-1-190770, JP-A-6-16982, JP-A-7-82499,    JP-A-8-34942, JP-A-8-60053, JP-A-8-113745, JP-A-8-310116,    JP-A-10-140063, JP-A-10-298463, JP-A-11-29729, JP-A-11-320921,    EP-A-173476, EP-A-468649, EP-A-559309, EP-A-596383, German Patent    3,411,476, U.S. Pat. No. 6,086,955, WO99/13009, British Patent    Publication 2,341,868A, etc. [for example,    Cu-Pc-(SO₃H)_(m)(SO₂NR₁R₂)_(n): a mixture of m+n=0 to 4, and m#0];-   (5) phthalocyanine-base dyes described in JP-A-60-208365,    JP-A-61-2772, JP-A-6-57653, JP-A-8-60052, JP-A-8-295819,    JP-A-10-130517, JP-A-11-72614, Japanese Unexamined Published    International Application Nos. 11-515047 and 11-515048, EP-A-196901,    WO95/29208, WO98/49239, W098/49240, W099/50363, W099/67334, etc.    [for example, Cu-Pc-(SO₃H)_(I)(SO₂NH₂)_(m)(SO₂NR₁R₂)_(n): a mixture    of l+m+n=0 to 4]; and-   (6) phthalocyanine-base dyes described in JP-A-59-22967,    JP-A-61-185576, JP-A-1-95093, JP-A-3-195783, EP-A-649881,    WO00/08101, WO00/08103, etc. [for example, Cu-Pc-(SO₂NR₁R₂)_(n): a    mixture of n=1 to 5].

Phthalocyanine-base dyes widely used in general at present, representedby Direct Blue 87 and Direct Blue 199, are excellent in the lightfastness as compared with generally known magenta dyes, yellow dyes andtriphenylmethane-base cyanine dyes.

However, the phthalocyanine-base dyes provide a greenish (color) hueunder acidic conditions and are improper for a cyan ink. In the case ofusing these dyes for a cyanine ink, these are most suitably used underconditions from neutral to alkaline. However, even if the ink is in theregion from neutral to alkaline, when the material on which an image orthe like is recorded is an acidic paper, the (color) hue of the printedmatter may greatly change.

Furthermore, discoloration to a greenish (color) hue or decolorationoccurs due to oxidative gases such as nitrogen oxide gas and ozone,which are often taken as a problem also from an environmental issue, andthis simultaneously causes reduction in the printing density.

On the other hand, triphenylmethane-base dyes provide a good (color) huebut are very inferior in the light fastness, resistance against ozonegas and the like.

If the use field hereafter expands and the printed matter is widely usedfor exhibition such as advertisement, the case of being exposed to lightor active gas in the environment increases and to cope with this, a dyeand an ink composition having light fastness and excellent resistanceagainst active gases (for example, oxidative gas such as NOx and ozone,and SOx) in the environment are more strongly demanded.

However, it is very difficult to find out a cyan dye (for example,phthalocyanine-base dye) and a cyan ink satisfying these requirements ina high level.

As for the ink for an ink jet recording system, an aqueous dye inkobtained by dissolving a water-soluble dye of various types in a liquidmedium comprising water and a water-soluble organic solvent, an aqueouspigment ink obtained by dispersing a pigment of various types in aliquid medium comprising water and a water-soluble organic solvent, anoily dye ink obtained by dissolving an oil-soluble dye in an organicsolvent, and the like are known. Among these inks, the aqueous inkobtained by dissolving an aqueous dye is excellent in the safety becausethe main solvent is water, enables good coloring of a color image andformation of a high-grade printed image because a dye is used, and alsoexhibits excellent ink storage stability. Therefore, this aqueous ink ispredominating as an ink for ink jet recording.

The phthalocyanine-base dyes imparted with water solubility areheretofore disclosed, for example, in WO00/08102, JP-A-2000-303014 andJP-A-2000-313837, however, none of these dyes have succeeded insatisfying both the (color) hue and the fastness to light and oxidativegas. A cyan ink product fully satisfying the requirements on the marketis not yet provided.

When a recorded image having a high optical density is formed, this isaccompanied with a problem that as the image is dried, the dye crystaldeposits on the surface of the recording material and the recorded imagereflects light to cause a so-called bronze phenomenon of emittingmetallic gloss. This phenomenon is considered to readily occur when thewater solubility of dye is decreased so as to improve water resistanceor an amino group of a hydrogen bond group is introduced into the dyestructure, because the dye is elevated in the associating (aggregating)property. The generation of bronze phenomenon not only incurs decreasein the optical density of the recorded image but also causes greatdifference from the desired (color) hue of the recorded image.Therefore, it is one of important performances required of the ink forink jetting to prevent the bronze phenomenon.

Known examples of the method for preventing the bronze phenomenoninclude a method of adding a specific nitrogen-containing compound (see,for example, JP-A-55-120676, JP-A-62-119280, JP-A-64-6072,JP-A-1-152176, JP-A-2-41369, JP-A-5-125311, JP-A-6-25575, JP-A-6-128515,JP-A-6-228476, JP-A-6-228483, JP-A-6-248212, JP-A-7-228810,JP-A-7-268261, JP-A-8-259865, JP-A-9-12944, JP-A-9-12946, JP-A-9-12949and JP-A-10-36735) and a method of adding a specific titanium compound(see, JP-A-8-337745). The bronze phenomenon may be prevented fromoccurring by adding these compounds, however, there is a fear that theadditives decrease various performances of ink and the quality ofrecorded image. For example, as described in JP-A-8-259865, when analkanolamine is added to the ink, the bronze phenomenon can be preventedbut by the addition only in a small amount, the pH of ink increases to11 or more and the high pH ink not only adversely affects nozzles butalso lacks in safety on erroneously contacting with a human body andmoreover, decreases the printing grade or water resistance of therecorded image.

Other than these, examples of the method for improving the performanceof ink for ink jetted by using an additive are described inJP-A-5-339532 and JP-A-2001-254040 where an anionic additive except fordyes, having lithium ion, cuaternary ammonium ion or quaternaryphosphonium ion as the counter cation is added and thereby, even whenthe counter ion of the dye is not such ion, an effect of preventingclogging is obtained because the solubility is improved. On the otherhand, JP-A-7-26178 describes a technique where an alkali metal compoundis added to ink and thereby, the production of an aggregate of dye isprevented, as a result, the viscosity of ink does not increase. However,in JP-A-1036735, it is pointed out that this improvement effect can beattained when the storage time is short, but when stored for a longperiod of time, the storage stability has a problem.

As such, various effects can be obtained by using additives, however,various performances can be hardly maintained if additives are used.Particularly, in the case where the solubility and aggregating propertyof dye must be taken account of, selection of the kind and amount ofadditive is difficult. In using an ionic additive, the effect thereof onthe counter ion must also be taken into consideration. Accordingly, asubstantial bronze phenomenon-inhibiting method not relying on additivesis preferred.

Studies are being aggressively made with an attempt to improve variousperformances required of the ink for ink jetting by changing the counterion for the ionic hydrophilic group of metal phthalocyanine compoundsand examples thereof include JP-A-5-339532, JP-A-6-16982, JP-A-6-248212,JP-A-6-322286, JP-A-7-138511 and JP-A-10-130517.

For example, in JP-A-57-202358, JP-A-63-81179, JP-A-63-317568 andJapanese Patents 2581769 and 3163176, lithium ion is referred to aspreferred counter ion for the ionic hydrophilic group of metalphthalocyanine dyes and it is stated that this ion is effective forproviding an ink having high concentration, storage stability andjetting stability. On the other hand, JP-A-7-82499 states that lithiumion is not preferred as the counter cation, because the water resistanceof the recorded image decreases due to high water solubility of the dye.From these, it is seen that the performances required of the ink for inkjetting cannot be easily satisfied merely by changing the counter salt.

As described above, an ink capable of satisfying all of variousperformances required of the water-soluble ink for ink jetting is notyet found at present.

Problems to be Solved by the Invention:

The present invention has been made to solve those problems inconventional techniques and achieve the following objects. That is, theobjects of the present invention are

(1) to provide a novel ink having absorption properties ensuringexcellent color reproduction as a dye for three primary colors and atthe same time, having sufficiently high fastness to light, heat,humidity and active gas in the environment;

(2) to provide an ink of giving a colored image or colored materialexcellent in the (color) hue and the fastness, for example, an inkcomposition for printing such as ink jetting;

(3) to provide an ink for ink jet recording and an ink jet recordingmethod, which can form an image having good (color) hue by the use of aphthalocyanine compound derivative, having high fastness particularlyagainst ozone gas and free of generation of a bronze phenomenon; and

(4) to provide a method for forming an image having fastness by usingthe above-described ink jet recording method and thereby improving theozone gas discoloration resistance of the image recorded material.

Means to Solve the Problems:

As a result of extensive investigations on phthalocyanine derivatives ofproviding good (color) hue, generating no bronze phenomenon and ensuringfastness to light and gas (particularly ozone gas), the presentinventors have found that the above-described objects can be attained bya phthalocyanine compound where the counter cation of the ionichydrophilic group is lithium ion, particularly a phthalocyanine compoundrepresented by the following formula (I), having (1) a specific spectralabsorption curve and (2) a specific dye structure (specific substituentsare introduced into specific substitution sites in a specific number ofsubstituents), more particularly, a phthalocyanine compound representedby formula (II) or (III).

Disclosure of the Invention:

The present invention has been accomplished based on this finding. Morespecifically, the objects of the present invention can be attained bythe following means.

1. An ink comprising a water-soluble phthalocyanine compound, wherein inthe spectral absorption curve of an aqueous solution of thephthalocyanine compound, the absorbance ratio b/a of the maximumabsorbance b in the absorption band of 660 to 680 nm and the maximumabsorbance a in the absorption band of 600 to 640 nm is less than 0.8and the counter ion for the ionic hydrophilic group of thephthalocyanine compound is lithium ion.

2. The ink as described in 1, wherein the water-soluble phthalocyaninecompound is represented by the following formula (I):

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ each independently representsa hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, analkenyl group, an aralkyl group, an aryl group, a heterocyclic group, acyano group, a hydroxyl group, a nitro group, an amino group, analkylamino group, an alkoxy group, an aryloxy group, an amido group, anarylamino group, a ureido group, a sulfamoylamino group, an alkylthiogroup, an arylthio group, an alkoxycarbonylamino group, a sulfonamidogroup, a carbamoyl group, a sulfamoyl group, a sulfonyl group, analkoxycarbonyl group, a heterocyclic oxy group, an azo group, an acyloxygroup, a carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group,an aryloxycarbonylamino group, an imido group, a heterocyclic thiogroup, a sulfinyl group, a phosphoryl group or an acyl group and eachmay further have a substituent;

W₁, W₂, W₃ and W₄ each independently represents the group represented byR₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈, a sulfonylsulfamoyl group or anacylsulfamoyl group and each may further have a substituent, providedthat at least one of W₁, W₂, W₃ and W₄ is an ionic hydrophilic group byitself or has an ionic hydrophilic group as a substituent, provided thatthe counter ion for the ionic hydrophilic group is lithium ion; l, m, nand p each represents an integer of 1 or 2; and M represents a hydrogenatom, a metal element, a metal oxide, a metal hydroxide or a metalhalide.

3. The ink as described in 2, wherein the formula (I) is represented bythe following formula (II):

wherein Z₁, Z₂, Z₃ and Z₄ each independently represents a substituted orunsubstituted alkyl group, a substituted or unsubstituted cycloalkylgroup, a substituted or . unsubstituted alkenyl group, a substituted orunsubstituted aralkyl group, a substituted or unsubstituted aryl groupor a substituted or unsubstituted heterocyclic group, q₁, q₂, q₃ and q₄each independently represents an integer of 1 or 2, a₃₁, a₃₂, a₃₃ anda₃₄ each independently represents an integer of 1 or 2, M has the samemeaning as M in formula (I), and at least one of Z₁, Z₂, Z₃ and Z₄ hasan ionic hydrophilic group as a substituent, provided that the counterion for the ionic hydrophilic group is lithium ion.

4. The ink as described in 2, wherein the formula (I) is represented bythe following formula (III):

wherein R₂₁, R₂₂, R₂₃ and R₂₄ each independently represents a hydrogenatom, a substituted or unsubstituted alkyl group, a substituted orunsubstituted cycloalkyl group, a substituted or unsubstituted alkenylgroup, a substituted or unsubstituted aralkyl group, a substituted orunsubstituted aryl group or a substituted or unsubstituted heterocyclicgroup, V₁₁, V₁₂, V₁₃ and V₁₄ each independently represents a substitutedor unsubstituted alkyl group, a substituted or unsubstituted cycloalkylgroup, a substituted or unsubstituted alkenyl group, a substituted orunsubstituted aralkyl group, a substituted or unsubstituted aryl group,or a substituted or unsubstituted heterocyclic group, M has the samemeaning as M in formula (I), and at least one of R₂₁, R₂₂, R₂₃, R₂₄,V₁₁, V₁₂, V₁₃ and V₁₄ has an ionic hydrophilic group as a substituent,provided that the counter ion for the ionic hydrophilic group is lithiumion.

5. The ink as described in 3, wherein in formula (II), q₁=q₂=q₃=q₄=2.

6. An ink for ink jetting, comprising the ink described in any one of 1to 5.

7. An ink jet recording method comprising forming an image on an imagereceiving material using the ink for ink jetting described in 6, theimage receiving material comprising a support having thereon an inkimage-receiving layer containing a white inorganic pigment particle.

8. A method for improving ozone gas discoloration of an image recordedmaterial, comprising forming an image using the ink described in 1 to 6.

9. A water-soluble phthalocyanine compound represented by the followingformula (IV):

wherein Z₁, Z₂, Z₃ and Z₄ each independently represents a substituted orunsubstituted alkyl group, a substituted or unsubstituted cycloalkylgroup, a substituted or unsubstituted alkenyl group, a substituted orunsubstituted aralkyl group, a substituted or unsubstituted aryl groupor a substituted or unsubstituted heterocyclic group, q₁, q₂, q₃ and q₄each independently represents an integer of 1 or 2, a₃₁, a₃₂, a₃₃ anda₃₄ each independently represents an integer of 1 or 2, M has the samemeaning as M in formula (I), and at least one of Z₁, Z₂, Z₃ and Z₄ hasan ionic hydrophilic group as a substituent, provided that the counterion for the ionic hydrophilic group is lithium ion.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention is described in detail below. The ink as used inthe present invention means a composition comprising a coloring materialsuch as dye or pigment and a dispersant (e.g., solvent) therefor and issuitably used particularly for image formation.

The water-soluble phthalocyanine compound for use in the presentinvention is characterized by having a specific spectral absorptioncurve (visible absorption spectrum) and having lithium ion as thecounter ion for the ionic hydrophilic group.

In order to grasp the relationship between the structure of cyanine andvarious performances such as (color) hue, fastness to light and ozonegas, and generation of bronze phenomenon, various phthalocyaninecompounds were synthesized and evaluated on the performance. As aresult, it has been found that when a phthalocyanine compound having aspecific spectral absorption curve and having lithium ion as the countercation for the ionic hydrophilic group is used, the image can beremarkably prevented from generation of a bronze phenomenon withoutimpairing the performances such as (color) hue and fastness.

The counter cation of the phthalocyanine compound for use in the presentinvention is lithium ion. It is not necessary that all counter cationsare lithium ion, but the counter cation present in a largest proportionmust be substantially lithium ion. With such a condition of the presenceproportion, alkali metal ion (e.g., sodium ion, potassium ion), alkalineearth metal ion (e.g., magnesium ion, calcium ion), quaternary ammoniumion, quaternary phosphonium ion, sulfonium ion or the like can becontained as the counter cation.

As for the kind and proportion of the counter cation in theabove-described phthalocyanine compound, the analysis methods andelements are described in Shin Jikken Kagaku Koza 9, Bunseki Kagaku(Lecture 9 of New Experiment Chemistry, Analysis Chemistry, compiled byNippon Kagaku Kai, Maruzen (1977) and Dai 4 Han, Jikken Kagaku Koza 15,Bunseki (4th Edition, Lecture 15 of Experiment Chemistry, Analysis),compiled by Nippon Kagaku Kai, Maruzen (1991). By referring to thesepublications, the analysis method can be selected and the analysis anddetermination can be made. In particular, the determination can beeasily performed by an analysis method such as ion chromatography,atomic absorption method or induction coupled plasma emission analysismethod (ICP).

The amount of lithium ion in the phthalocyanine compound is 50% or more,preferably 60% or more, more preferably 80% or more, still morepreferably 90% or more, with a preferred upper limit of 100%, based onthe entire counter ion.

The phthalocyanine compound of the present invention having lithium ionas the counter cation may be obtained by any method. Examples of themethod include (1) a method of converting the counter cation intolithium ion from other cation using ion exchange resin, (2) a method ofdepositing lithium ion with acid or salt from a system containinglithium ion, (3) a method of forming phthalocyanine using a raw materialor synthesis intermediate where the counter cation is lithium ion, (4) amethod of converting the functional group of a phthalocyanine compoundusing a reacting agent where the counter cation is lithium ion, andthereby introducing an ionic hydrophilic group, and (5) a method ofsynthesizing a compound where the counter cation for the ionichydrophilic group on a phthalocyanine compound is silver ion, reactingthe compound with a lithium halide solution, and removing theprecipitated silver halide, thereby changing the counter cation tolithium ion.

Examples of the ionic hydrophilic group in the phthalocyanine compoundinclude a sulfo group (—SO₃ ⁻X⁺), a carboxyl group (—CO₂ ⁻X⁺), aquaternary ammonium group (—N⁺RR′R″X³¹) , an acylsulfamoyl group(—SO₂N⁻X⁺COR), a sulfonylcarbamoyl group (—CON⁻X⁺SO₂—R) and asulfonyl-sulfamoyl group (—SO₂N⁻X⁺SO₂—R). In the present invention, inorder to have lithium ion as the counter cation, an anionic hydrophilicgroup must be present. The ionic hydrophilic group is preferably a sulfogroup or a carboxyl group, more preferably a sulfo group. In theparentheses above, X⁺ represents a counter ion and R, R′ and R″ eachrepresents a substituent.

The phthalocyanine compound for use in the present invention is acompound where in the spectral absorption curve of an aqueous solutionthereof, the absorbance ratio b/a of the maximum absorbance b in theabsorption band of 660 to 680 nm and the maximum absorbance a in theabsorption band of 600 to 640 nm is less than 0.8 and the counter ionfor the ionic hydrophilic group of the phthalocyanine compound islithium ion.

The absorbance ratio as used in the present invention indicates anabsorbance ratio obtained under the following conditions. That is, thespectral absorption curve of a solution obtained by 1,000-fold dilutinga 2 wt % aqueous solution of phthalocyanine compound with distilledwater is determined using a spectrophotometer according to thedefinition of JIS Z8120-86 by selecting the measuring temperature fromthe range of 15 to 30° C. and setting the measurement cell length to 10mm. The ratio b/a of the maximum absorbance b in the absorption band of660 to 680 nm on the determined spectral absorption curve and themaximum absorbance a in the absorption band of 600 to 640 nm is used asthe absorbance ratio.

The absorbance ratio b/a under the conditions specified in the presentinvention can be easily determined by reading the maximum absorbance aat 600 to 640 nm and the maximum absorbance b at 660 to 680 nm using theabove-described spectrophotometer, measurement cell length and pHcondition. Incidentally, the distilled water used for the preparation ordilution of the aqueous solution is a distilled water at a pH of 5 to 8.

The aqueous phthalocyanine compound having a specific spectralabsorption property value (an absorbance ratio b/a value of less than0.8) is very important in improving the fastness of the formed image.

More specifically, the maximum absorbance b in the absorption band from660 to 680 nm and the maximum absorbance b in the absorption band from600 to 640 nm on the spectral absorption curve obtained by measuring anaqueous solution of a water-soluble phthalocyanine compound using aspectrophotometer according to JIS Z8120-86 are attributable to theabsorption of monomer and the absorption of aggregate, respectively. Theabsorbance ratio b/a value therebetween participates in the fastness ofthe formed image. The absorbance ratio b/a value is preferably from 0.3to less than 0.75, more preferably from 0.4 to 0.65.

The aggregate of water-soluble phthalocyanine compound as used in thepresent invention means an aggregate formed by two or morephthalocyanine molecules. When the aggregate of phthalocyanine compoundis used, stability against light, heat and oxidative gas (particularlyozone gas) is remarkably improved as compared with the compound in themonomolecular dispersion state. Furthermore, by the formation of anaggregate, the cyan (color) hue in the absorption spectrum (excellent.absorption property as a cyan dye for image forming materials) isgreatly changed for the better.

Whether or not the dye is aggregated can be easily determined from theshift of absorption maximum (λmax) in the absorption spectrum asdescribed, for example, in J. D. Wright (translated by Taro Eguchi),Bunshi Kessho (Molecular Crystal), Kagaku Dojin. In general, theaggregate is classified into two aggregates, namely, J-aggregate whichshifts to the long wave side, and H-aggregate which shifts to the shortwave side. In the present invention, an aggregate is formed by theshifting of the absorption maximum to the short wave side and thisaggregate is used as the water-soluble phthalocyanine aggregate.

The phthalocyanine compound for use in the present invention may haveany structure insofar as the spectral absorption curve of the aqueoussolution satisfies the requirements of the present invention and thecompound contains an ionic hydrophilic group having lithium ion as thecounter cation, however, a compound represented by formula (I) ispreferred.

In formula (I) , R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ each independentlyrepresents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkylgroup, an alkenyl group, an aralkyl group, an aryl group, a heterocyclicgroup, a cyano group, a hydroxyl group, a nitro group, an amino group,an alkylamino group, an alkoxy group, an aryloxy group, an amido group,an arylamino group, a ureido group, a sulfamoylamino group, an alkylthiogroup, an arylthio group, an alkoxycarbonylamino group, a sulfonamidogroup, a carbamoyl group, a sulfamoyl group, a sulfonyl group, analkoxycarbonyl group, a heterocyclic oxy group, an azo group, an acyloxygroup, a carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group,an aryloxycarbonylamino group, an imido group, a heterocyclic thiogroup, a sulfinyl group, a phosphoryl group or an acyl group and eachmay further have a substituent.

R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ each is preferably a hydrogen atom, ahalogen atom, an alkyl group, an aryl group, a cyano group, an alkoxygroup, an amido group, a ureido group, a sulfonamido group, a carbamoylgroup, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group or asulfinyl group, more preferably a hydrogen atom, a halogen atom or acyano group, and most preferably a hydrogen atom.

W₁, W₂, W₃ and W₄ each independently represents a halogen atom, an alkylgroup, a cycloalkyl group, an alkenyl group, an aralkyl group, an arylgroup, a heterocyclic group, a cyano group, a hydroxyl group, a nitrogroup, an amino group, an alkylamino group, an alkoxy group, an aryloxygroup, an amido group, an arylamino group, a ureido group, asulfamoylamino group, an alkylthio group, an arylthio group, analkoxycarbonylamino group, a sulfonamido group, a carbamoyl group, asulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, aheterocyclic oxy group, an azo group, an acyloxy group, a carbamoyloxygroup, a silyloxy group, an aryloxycarbonyl group, anaryloxycarbonylamino group, an imido group, a heterocyclic thio group, asulfinyl group, a phosphoryl group, an acyl group, a sulfonylsulfamoylgroup or an acylsulfamoyl group and each may further have a substituent.

W₁, W₂, W₃ and W₄ is preferably an acyl group having from 2 to 12 carbonatoms, an acyloxy group having from 2 to 12 carbon atoms, a carbamoylgroup having from 1 to 12 carbon atoms, an alkyloxycarbonyl group havingfrom 2 to 12 carbon atoms, an aryloxycarbonyl group having from 7 to 18carbon atoms, a cyano group, a nitro group, an alkylsulfinyl grouphaving from 1 to 12 carbon atoms, an arylsulfonyl group having from 6 to18 carbon atoms, an alkylsulfonyl group having from 1 to 12 carbonatoms, an arylsulfonyl group having from 6 to 18 carbon atoms, asulfamoyl group having from 0 to 12 carbon atoms, an halogenated alkylgroup having from 1 to 12 carbon atoms, a halogenated alkyloxy grouphaving from 1 to 12 carbon atoms, a halogenated alkylthio group havingfrom 1 to 12 carbon atoms, a halogenated aryloxy group having from 7 to18 carbon atoms, an aryl group having from 7 to 18 carbon atoms, or a5-, 6-, 7- or 8-membered heterocyclic group having from 1 to 18 carbonatoms and containing a nitrogen atom, an oxygen atom or a sulfur atom.

W₁, W₂, W₃ and W₄ is more preferably an alkylsulfonyl group having from1 to 12 carbon atoms, an arylsulfonyl group having from 6 to 18 carbonatoms or a sulfamoyl group having from 0 to 12 carbon atoms.

W₁, W₂, W₃ and W₄ is still more preferably an alkylsulfonyl group havingfrom 1 to 12 carbon atoms or a sulfamoyl group having from 0 to 12carbon atoms, and most preferably an alkylsulfonyl group having from 1to 12 carbon atoms.

At least one of the groups represented by W₁, W₂, W₃ and W₄ is an ionichydrophilic group by itself or has an ionic hydrophilic group as asubstituent.

Examples of the ionic hydrophilic group as a substituent include a sulfogroup, a carboxyl group, a quaternary ammonium group, an acylsulfamoylgroup, a sulfonylcarbamoyl group and a sulfonylsulfamoyl group. Amongthese, preferred are a carboxyl group, a sulfo group and asulfonylsulfamoyl group, more preferred is a sulfo group. The countercation for the ionic hydrophilic group is lithium ion.

l, m, n and p each independently represents an integer of 1 or 2preferably satisfying 4≦l+m+n+p≦8, more preferably 4≦l+m+n+p≦6, and mostpreferably each is 1 (l=m=n=p=1).

M represents a hydrogen atom, a metal element, a metal oxide, a metalhydroxide or a metal halide.

M is preferably a hydrogen atom, a metal atom such as Li, Na, K. Mg, Ti,Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu,Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb and Bi, a metal oxidesuch as VO and GeO, a metal hydroxide such as Si(OH) ₂, Cr(OH) ₂ andSn(OH) ₂, or a metal halide such as AlCl, SiCl₂, VCl, VCl₂, VOCl, FeCl,GaCl and ZrCl, more preferably Cu, Ni, An or Al, and most preferably Cu.

In the phthalocyanine compound represented by formula (I), thephthalocyanine ring (Pc) may form a dimer (for example, Pc-M-L-M-Pc) ora trimer through a divalent linking group (L) and the plurality of M'smay be the same or different.

The divalent linking group represented by L is preferably an oxy group—O—, a thio group —S—, a carbonyl group —CO—, a sulfonyl group —SO₂—, animino group —NH—, a methylene group —CH₂— or a group formed by combiningtwo or more of these groups.

Those substituents R₁, R₂, R₃, R₄, R₅,R₆, R₇, R₈, W₁, W₂, W₃ and W₄ eachmay further have the following substituent if it is a group which canfurther have a substituent.

Examples of the substituent which is further substituted include ahalogen atom (e.g., chlorine, bromine), a linear or branched alkyl grouphaving from 1 to 12 carbon atoms, an aralkyl group having from 7 to 18carbon atoms, an alkenyl group having from 2 to 12 carbon atoms, alinear or branched alkynyl group having from 2 to 12 carbon atoms, acycloalkyl group having from 3 to 12 carbon atoms, which may have a sidechain, and a cycloalkenyl group having from 3 to 12 carbon atoms, whichmay have a side chain, more specifically an alkyl group (e.g., methyl,ethyl, propyl, isopropyl, tert-butyl, 2-methanesulfonylethyl,3-phenoxypropyl, trifluoromethyl, cyclopentyl), an aryl group (e.g.,phenyl, 4-tert-butylphenyl, 2,4-di-tert-amylphenyl), a heterocyclicgroup (e.g., imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl,2-pyrimidinyl, 2-benzothiazolyl), a cyano group, a hydroxyl group, anitro group, a carboxy group, an amino group, an alkyloxy group (e.g.,methoxy, ethoxy, 2-methoxyethoxy, 2-methanesulfonylethoxy), an aryloxygroup (e.g., phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy,3-nitrophenoxy, 3-tert-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), anacylamino group (e.g., acetamido, benzamido,4-(3-tert-butyl-4-hydroxyphenoxy)butanamido), an alkylamino group (e.g.,methylamino, butylamino, diethylamino, methylbutyl-amino), an anilinogroup (e.g., phenylamino, 2-chloro-anilino), a ureido group (e.g.,phenylureido, methylureido, N,N-dibutylureido), a sulfamoylamino group(e.g., N,N-dipropylsulfamoylamino), an alkylthio group (e.g.,methylthio, octylthio, 2-phenoxyethylthio), an arylthio group (e.g.,phenylthio, 2-butoxy-5-tert-octylphenylthio, 2-carboxyphenylthio), analkyloxycarbonylamino group (e.g., methoxycarbonylamino), a sulfonamidogroup (e.g., methane-sulfonamido, benzenesulfonamido,p-toluenesulfonamido), a carbamoyl group (e.g., N-ethylcarbamoyl,N,N-dibutyl-carbamoyl), a sulfamoyl group (e.g., N-ethylsulfamoyl,N,N-dipropylsulfamoyl, N,N-diethylsulfamoyl), a sulfonyl group (e.g.,methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), analkyloxycarbonyl group (e.g., methoxycarbonyl, butyloxycarbonyl), aheterocyclic oxy group (e.g., 1-phenyltetrazol-5-oxy,2-tetrahydropyranyloxy), an azo group (e.g., phenylazo,4-methoxyphenylazo, 4-pivaloylaminophenylazo,2-hydroxy-4-propanoylphenylazo), an acyloxy group (e.g., acetoxy), acarbamoyloxy group (e.g., N-methylcarbamoyloxy, N-phenylcarbamoyloxy), asilyloxy group (e.g., trimethyl-silyloxy, dibutylmethylsilyloxy), anaryloxycarbonylamino group (e.g., phenoxycarbonylamino), an imido group(e.g., N-succinimido, N-phthalimido), a heterocyclic thio group (e.g.,2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio,2-pyridylthio), a sulfinyl group (e.g., 3-phenoxy-propylsulfonyl), aphosphonyl group (e.g., phenoxy-phosphonyl, octyloxyphosphonyl,phenylphosphonyl), an aryloxycarbonyl group (e.g., phenoxycarbonyl), anacyl group (e.g., acetyl, 3-phenylpropanoyl, benzoyl), an ionichydrophilic group (e.g., carboxyl, sulfo, quaternary ammonium,sulfonylsulfamoyl, acylsulfamoyl), a cyano group, a hydroxyl group, anitro group, a carboxyl group and an amino group.

Examples of the halogen atom represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇,R₈, W₁, W₂, W₃ and W₄ include a fluorine atom, a chlorine atom and abromine atom.

The alkyl group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁, W₂,W₃ and W₄ includes an alkyl group having a substituent and anunsubstituted alkyl group. The alkyl group is preferably an alkyl grouphaving from 1 to 12 carbon atoms excluding the substituent. Examples ofthe substituent include a hydroxyl group, an alkoxy group, a cyanogroup, a halogen atom and an ionic hydrophilic group. Examples of thealkyl group include a methyl group, an ethyl group, a butyl group, anisopropyl group, a tert-butyl group, a hydroxyethyl group, amethoxyethyl group, a cyanoethyl group, a trifluoromethyl group, a3-sulfopropyl group and a 4-sulfobutyl group.

The cycloalkyl group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁,W₂, W₃. and W₄ includes a cycloalkyl group having a substituent and anunsubstituted cycloalkyl group. The cycloalkyl group is preferably acycloalkyl group having from 5 to 12 carbon atoms excluding thesubstituent. Examples of the substituent include an ionic hydrophilicgroup. Examples of the cycloalkyl group include a cyclohexyl group.

The alkenyl group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁, W₂,W₃ and W₄ includes an alkenyl group having a substituent and anunsubstituted alkenyl group. The alkenyl group is preferably an alkenylgroup having from 2 to 12 carbon atoms excluding the substituent.Examples of the substituent include an ionic hydrophilic group. Examplesof the alkenyl group include a vinyl group and an alkyl group.

The aralkyl group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁, W₂,W₃ and W₄ include an aralkyl group having a substituent and anunsubstituted aralkyl group. The aralkyl group is preferably an aralkylgroup having from 7 to 12 carbon atoms excluding the substituent.Examples of the substituent include an ionic hydrophilic group. Examplesof the aralkyl group include a benzyl group and a 2-phenethyl group.

The aryl group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁, W₂, W₃and W₄ includes an aryl group having a substituent and an unsubstitutedaryl group. The aryl group is preferably an aryl group having from 6 to12 carbon atoms excluding the substituent. Examples of the substituentinclude an alkyl group, an alkoxy group, a halogen atom, an alkylaminogroup and an ionic hydrophilic group. Examples of the aryl group includea phenyl group, a p-tolyl group, a p-methoxyphenyl group, ano-chlorophenyl group and an m-(3-sulfopropylamino)phenyl group.

The heterocyclic group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈,W₁, W₂, W₃ and W₄ includes a heterocyclic group having a substituent andan unsubstituted heterocyclic group. The heterocyclic group may be eachindependently a saturated heterocyclic ring or an unsaturatedheterocyclic ring. Furthermore, the heterocyclic group may eachindependently form a condensed ring with other ring. The heterocyclicgroup is preferably a 5- or 6-membered heterocyclic group.

Examples of the heterocyclic group represented by R₁, R₂, R₃, R₄, R₅,R₆, R₇, R₈, W₁, W₂, W₃ and W₄ are shown below in the form of aheterocyclic ring by omitting the substitution site. The substitutionsite is not limited and for example, pyridine may be substituted at the2-position, 3-position or 4-position. Examples of the heterocyclic groupinclude pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline,isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole,benzopyrrole, indole, furan, benzofuran, thiophene, benzothiophene,pyrazole, benzopyrazole, imidazole, benzimidazole, triazole, oxazole,benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole,thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine,piperazine, imidazolidine and thiazoline. In particular, aromaticheterocyclic groups are preferred. Preferred examples thereof, shown inthe same manner as above, include pyridine, pyrazine, pyrimidine,pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole,thiazole, benzothiazole, isothiazole, benzisothiazole and thiadiazole.

In the case where the heterocyclic group represented by R₁, R₂, R₃, R₄,R₅, R₆, R₇, R₈, W₁, W₂, W₃ and W₄ further has a substituent, examples ofthe substituent include an alkyl group (R—), an alkoxy group (RO—), analkylamino group (RNH-, RR′N-), a carbamoyl group (-CONHR), a sulfamoylgroup (-SO₂NHR), a sulfonylamino group (—NHSO₂R), a halogen atom and anionic hydrophilic group (R and R′ each represents an alkyl group or aphenyl group and may further have an ionic hydrophilic group).

The alkylamino group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁,W₂, W₃ and W₄ include an alkylamino group having a substituent and anunsubstituted alkylamino group. The alkylamino group is preferably analkylamino group having from 1 to 6 carbon atoms excluding thesubstituent. Examples of the substituent include an ionic hydrophilicgroup. Examples of the alkylamino group include a methylamino group anda diethylamino group.

The alkoxy group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁, W₂,W₃ and W₄ includes an alkoxy group having a substituent and anunsubstituted alkoxy group. The alkoxy group is preferably an alkoxygroup having from 1 to 12 carbon atoms excluding the substituent.Examples of the substituent include an alkoxy group, a hydroxyl groupand an ionic hydrophilic group. Examples of the alkoxy group include amethoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxygroup, a hydroxyethoxy group and a 3-carboxypropoxy group.

The aryloxy group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁, W₂,W₃ and W₄ includes an aryloxy group having a substituent and anunsubstituted aryloxy group. The aryloxy group is preferably an aryloxygroup having from 6 to 12 carbon atoms excluding the substituent.Examples of the substituent include an alkoxy group and an ionichydrophilic group. Examples of the aryloxy group include a phenoxygroup, a p-methoxyphenoxy group and an o-methoxyphenoxy group.

The amido group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁, W₂,W₃ and W₄ includes an amido group having a substituent and anunsubstituted amido group. The amido group is preferably an amido grouphaving from 2 to 12 carbon atoms excluding the substituent. Examples ofthe substituent include an ionic hydrophilic group. Examples of theamido group include an acetamido group, a propionamido group, abenzamido group and a 3,5-disulfobenzamido group.

The arylamino group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁,W₂, W₃ and W₄ includes an arylamino group having a substituent and anunsubstituted arylamino group. The arylamino group is preferably anarylamino group having from 6 to 12 carbon atoms excluding thesubstituent. Examples of the substituent include a halogen atom and anionic hydrophilic group. Examples of the arylamino group include ananilino group and a 2-chloroanilino group.

The ureido group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁, W₂,W₃ and W₄ includes a ureido group having a substituent and anunsubstituted ureido group. The ureido group is preferably a ureidogroup having from 1 to 12 carbon atoms excluding the substituent.Examples of the substituent include an alkyl group and an aryl group.Examples of the ureido group include a 3-methylureido group, a3,3-dimethylureido group and a 3-phenylureido group.

The sulfamoylamino group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈,W₁, W₂, W₃ and W₄ includes a sulfamoylamino group having a substituentand an unsubstituted sulfamoyl-amino group. Examples of the substituentinclude an alkyl group. Examples of the sulfamoylamino group include anN,N-dipropylsulfamoylamino group.

The alkylthio group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁,W₂, W₃ and W₄ includes an alkylthio group having a substituent and anunsubstituted alkylthio group. The alkylthio group is preferably analkylthio group having from 1 to 12 carbon atoms excluding thesubstituent. Examples of the substituent include an ionic hydrophilicgroup. Examples of the alkylthio group include a methylthio group and anethylthio group.

The arylthio group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁,W₂, W₃ and W₄ includes an arylthio group having a substituent and anunsubstituted arylthio group. The arylthio group is preferably anarylthio group having from 6 to 12 carbon atoms excluding thesubstituent. Examples of the substituent include an alkyl group and anionic hydrophilic group. Examples of the arylthio group include aphenylthio group and a p-tolylthio group.

The alkoxycarbonylamino group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇,R₈, W₁, W₂, W₃ and W₄ includes an alkoxycarbonylamino group having asubstituent and an unsubstituted alkoxycarbonylamino group. Thealkoxy-carbonylamino group is preferably an alkoxycarbonylamino grouphaving from 2 to 12 carbon atoms excluding the substituent. Examples ofthe substituent include an ionic hydrophilic group. Examples of thealkoxycarbonylamino group include an ethoxycarbonylamino group.

The sulfonamido group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁,W₂, W₃ and W₄ includes a sulfonamido group having a substituent and anunsubstituted sulfonamido group. The sulfonamido group is preferably ansulfonamido group having from 1 to 12 carbon atoms excluding thesubstituent. Examples of the substituent include an ionic hydrophilicgroup. Examples of the sulfonamido group include methanesulfonamido,benzenesulfonamido and 3-carboxybenzenesulfonamido.

The carbamoyl group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁,W₂, W₃ and W₄ includes a carbamoyl group having a substituent and anunsubstituted carbamoyl group. Examples of the substituent include analkyl group. Examples of the carbamoyl group include a methylcarbamoylgroup and a dimethylcarbamoyl group.

The sulfamoyl group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁,W₂, W₃ and W₄ includes a sulfamoyl group having a substituent and anunsubstituted sulfamoyl group. Examples of the substituent include analkyl group and an aryl group. Examples of the sulfamoyl group include adimethylsulfamoyl group, a di-(2-hydroxyethyl) sulfamoyl group and aphenylsulfamoyl group.

The sulfonyl group represented by R₁, R₂, R₃, R₄, R₅, R₆₁ R₇, R₈, W₁,W₂, W₃ and W₄ includes a sulfonyl group having a substituent and anunsubstituted sulfonyl group. Examples of the substituent include analkyl group and an aryl group. Examples of the sulfonyl group include amethanesulfonyl group and a phenylsulfonyl group.

The alkoxycarbonyl group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈,W₁, W₂, W₃ and W₄ includes an alkoxycarbonyl group having a substituentand an unsubstituted alkoxycarbonyl group. The alkoxycarbonyl group ispreferably an alkoxycarbonyl group having from 2 to 12 carbon atomsexcluding the substituent. Examples of the substituent include an ionichydrophilic group. Examples of the alkoxycarbonyl group include amethoxycarbonyl group and an ethoxycarbonyl group.

The heterocyclic oxy group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇,R₈, W₁, W₂, W₃ and W₄ includes a heterocyclic oxy group having asubstituent and an unsubstituted heterocyclic oxy group. Theheterocyclic oxy group is preferably a heterocyclic oxy group having a5- or 6-membered heterocyclic ring. Examples of the substituent includea hydroxyl group and an ionic hydrophilic group. Examples of theheterocyclic oxy group include a 2-tetrahydropyranyloxy group.

The azo group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁, W₂, W₃and W₄ includes an azo group having a substituent and an unsubstitutedazo group. Examples of the azo group include a p-nitrophenylazo group.

The acyloxy group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁, W₂,W₃ and W₄ includes an acyloxy group having a substituent and anunsubstituted acyloxy group. The acyloxy group is preferably an acyloxygroup having from 1 to 12 carbon atoms excluding the substituent.Examples of the substituent include an ionic hydrophilic group. Examplesof the acyloxy group include an acetoxy group and a benzoyloxy group.

The carbamoyloxy group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈,W₁, W₂, W₃ and W₄ includes a carbamoyloxy group having a substituent andan unsubstituted carbamoyloxy group. Examples of the substituent includean alkyl group. Examples of the carbamoyloxy group include anN-methylcarbamoyloxy group.

The silyloxy group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁,W₂, W₃ and W₄ includes a silyloxy group having a substituent and anunsubstituted silyloxy group. Examples of the substituent include analkyl group. Examples of the silyloxy group include a trimethylsilyloxygroup.

The aryloxycarbonyl group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈,W₁, W₂, W₃ and W₄ includes an aryloxycarbonyl group having a substituentand an unsubstituted aryloxycarbonyl group. The aryloxycarbonyl group ispreferably an aryloxycarbonyl group having from 7 to 12 carbon atomsexcluding the substituent. Examples of the substituent include an ionichydrophilic group. Examples of the aryloxycarbonyl group include aphenoxycarbonyl group.

The aryloxycarbonylamino group represented by R₁, R₂, R₃, R₄, R₅, R₆,R₇, R₈, W₁, W₂, W₃ and W₄ includes an aryloxycarbonylamino group havinga substituent and an unsubstituted aryloxycarbonylamino group. Thearyloxy-carbonylamino group is preferably an aryloxycarbonylamino grouphaving from 7 to 12 carbon atoms excluding the substituent. Examples ofthe substituent include an ionic hydrophilic group. Examples of thearyloxycarbonylamino group include a phenoxycarbonylamino group.

The imido group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁, W₂,W₃ and W₄ includes an imido group having a substituent and anunsubstituted imido group. Examples of the imido group include anN-phthalimido group and an N-succinimido group.

The heterocyclic thio group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇,R₈, W₁, W₂, W₃ and W₄ includes a heterocyclic thio group having asubstituent and an unsubstituted heterocyclic thio group. Theheterocyclic thio group preferably has a 5- or 6-membered heterocyclicring. Examples of the substituent include an ionic hydrophilic group.Examples of the heterocyclic thio group include a 2-pyridylthio group.

The sulfinyl group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁,W₂, W₃ and W₄ includes a sulfinyl group having a substituent and anunsubstituted sulfinyl group. Examples of the substituent include analkyl group and an aryl group. Examples of the sulfinyl group include aphenylsulfinyl group.

The phosphoryl group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁,W₂, W₃ and W₄ includes a phosphoryl group having a substituent and anunsubstituted phosphoryl group. Examples of the phosphoryl group includea phenoxy-phosphoryl group and a phenylphosphoryl group.

The acyl group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, W₁, W₂, W₃and W₄ includes an acyl group having a substituent and an unsubstitutedacyl group. The acyl group is preferably an acyl group having from 1 to12 carbon atoms. Examples of the substituent include an ionichydrophilic group. Examples of the acyl group include an acetyl groupand a benzoyl group.

The sulfonylsulfamoyl group represented by W₁, W₂, W₃ and W₄ includes asulfonylsulfamoyl group having a substituent and an unsubstitutedsulfonylsulfamoyl group. The sulfonylsulfamoyl group is preferably asulfonyl-sulfamoyl group having from 1 to 12 carbon atoms excluding thesubstituent. Examples of the substituent include an ionic hydrophilicgroup. Examples of the sulfonylsulfamoyl group include amethanesulfonylsulfamoyl group and a benzenesulfonylsulfamoyl group.

The acylsulfamoyl group represented by W₁, W₂, W₃ and W₄ includes anacylsulfamoyl group having a substituent and an unsubstitutedacylsulfamoyl group. The acylsulfamoyl group is preferably anacylsulfamoyl group having from 1 to 12 carbon atoms excluding thesubstituent. Examples of the substituent include an ionic hydrophilicgroup. Examples of the acylsulfamoyl group include an acetylsulfamoylgroup and a benzoylsulfamoyl group.

In the phthalocyanine compound represented by formula (I), the followingcombination is particularly preferred.

(i) R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ each is independently a hydrogenatom, a halogen atom or a cyano group, more preferably a hydrogen atomor a halogen atom, and most preferably a hydrogen atom.

(ii) W₁, W2, W₃ and W₄ each is a sulfamoyl, sulfonyl, sulfinyl,sulfonylsulfamoyl or acylsulfamoyl group having a substituent, and mostpreferably a sulfamoyl group or a sulfonyl group. Furthermore, at leastone of W₁, W₂, W₃ and W₄ has an ionic hydrophilic group as thesubstituent. In particular, most preferred is the case where W₁, W₂, W₃and W₄ each independently has an ionic hydrophilic group as thesubstituent. The ionic hydrophilic group as the substituent is a sulfogroup, a carboxyl group, a quaternary ammonium group, asulfonylsulfamoyl group or an acylsulfamoyl group, more preferably asulfo group, a sulfonylsulfamoyl group or an acylsulfamoyl group, stillmore preferably a sulfo group. The counter cation of the ionichydrophilic group is lithium ion.

(iii) l, m, n and p each is independently an integer of 1 or 2, morepreferably 1.

-   -   (iv) M is a hydrogen atom, a metal element, a metal oxide, a        metal hydroxide or a metal halide, more preferably Cut Ni, Zn or        Al, and most preferably Cu.

The phthalocyanine compound represented by formula (I) has at least oneor more ionic hydrophilic group within the molecule and therefore,exhibits good solubility or dispersibility in an aqueous medium.

From this viewpoint, the phthalocyanine compound represented by formula(I) preferably has at least four or more ionic hydrophilic groups withinone molecule and at least one of the plurality of ionic hydrophilicgroups is preferably a sulfo group. In particular, a phthalocyaninecompound having at least four or more sulfo groups within one moleculeis most preferred.

As for the combination of preferred substituents in the compoundrepresented by formula (I), a compound where at least one of varioussubstituents is the preferred group is preferred, and a compound whereall substituents are the preferred groups is most preferred.

Among the phthalocyanine compounds represented by formula (I), aphthalocyanine compound having a structure represented by the followingformula (II) or (III) is preferred. The phthalocyanine compoundrepresented by formula (II) or (III) of the present invention isdescribed in detail below.

Formula (II) is described below. Z₁, Z₂, Z₃ and Z₄ each independentlyrepresents a substituted or unsubstituted alkyl group, a substituted orunsubstituted cyclo-alkyl group, a substituted or unsubstituted alkenylgroup, a substituted or unsubstituted aralkyl group, a substituted orunsubstituted aryl group or a substituted or unsubstituted heterocyclicgroup, preferably a substituted alkyl group, a substituted aryl group ora substituted heterocyclic group, most preferably a substituted alkylgroup.

The alkyl group represented by Z₁, Z₂, Z₃ and Z₄ has the same meaning asthe alkyl group represented by R₁ to R₈ and W₁ to W₄ of formula (I).

The cycloalkyl group represented by Z₁, Z₂, Z₃ and Z₄ has the samemeaning as the cycloalkyl group represented by R₁ to R₈ and W₁ to W₄ offormula (I).

The alkenyl group represented by Z₁, Z₂, Z₃ and Z₄ has the same meaningas the alkenyl group represented by R₁ to R₈ and W₁ to W₄ of formula(I).

The aralkyl group represented by Z₁, Z₂, Z₃ and Z₄ has the same meaningas the aralkyl group represented by R₁ to R₈ and W₁ to W₄ of formula(I).

The aryl group represented by Z₁, Z₂, Z₃ and Z₄ has the same meaning asthe aryl group represented by R₁ to R₈ and W₁ to W₄ of formula (I).

The heterocyclic group represented by Z₁, Z₂, Z₃ and Z₄ has the samemeaning as the heterocyclic group represented by R₁ to R₈ and W₁ to W₄of formula (I).

q₁, q₂, q₃ and q₄ each independently represents an integer of 1 or 2,preferably 2, most preferably q₁=q₂=q₃=q₄=2.

a₃₁, a₃₂, a₃₃ and a₃₄ each independently represents an integer of 1 or2, preferably 1, most preferably a₃₁=a₃₂=a₃₃=a₃₄=1.

M has the same meaning as M in formula (I).

At least one of Z₁, Z₂, Z₃ and Z₄ has an ionic hydrophilic group as asubstituent.

Examples of the ionic hydrophilic group are the same as examples of theionic hydrophilic group in formula (I), and preferred examples are alsothe same.

The molecular weight of the phthalocyanine compound of the presentinvention is preferably from 750 to 2,500, more preferably from 995 to2,500, still more preferably from 995 to 2,000, particularly preferablyfrom 995 to 1,800.

Formula (III) is described below. R₂₁, R₂₂, R₂₃ and R₂₄ eachindependently represents a hydrogen atom, a substituted or unsubstitutedalkyl group, a substituted or unsubstituted cycloalkyl group, asubstituted or unsubstituted alkenyl group, a substituted orunsubstituted aralkyl group, a substituted or unsubstituted aryl groupor a substituted or unsubstituted heterocyclic group, preferably ahydrogen atom, a substituted alkyl group, a substituted aryl group or asubstituted heterocyclic group, more preferably a hydrogen atom or asubstituted alkyl group, and most preferably a hydrogen atom.

V₁₁, V₁₂, V₁₃ and V₁₄ each independently represents a substituted orunsubstituted alkyl group, a substituted or unsubstituted cycloalkylgroup, a substituted or unsubstituted alkenyl group, a substituted orunsubstituted aralkyl group, a substituted or unsubstituted aryl group,or a substituted or unsubstituted heterocyclic group, preferably asubstituted alkyl group, a substituted aryl group or a substitutedheterocyclic group, most preferably a substituted alkyl group.

The alkyl group represented by R₂₁, R₂₂, R₂₃, R₂₄, V₁₁, V₁₂, V₁₃ and V₁₄has the same meaning as the alkyl group represented by R₁ to R₈ and W₁to W₄ of formula (I).

The cycloalkyl group represented by R₂₁, R₂₂, R₂₃, R₂₄, V₁₁, V₁₂, V₁₃and V₁₄ has the same meaning as the cycloalkyl group represented by R₁to R₈ and W₁ to W₄ of formula (I).

The alkenyl group represented by R₂₁, R₂₂, R₂₃, R₂₄, V₁₁, V₁₂, V₁₃ andV₁₄ has the same meaning as the alkenyl group represented by R₁ to R₈and W₁ to W₄ of formula (I).

The aralkyl group represented by R₂₁, R₂₂, R₂₃, R₂₄, V₁₁, V₁₂, V₁₃ andV₁₄ has the same meaning as the aralkyl group represented by R₁ to R₈and W₁ to W₄ of formula (I).

The aryl group represented by R₂₁, R₂₂, R₂₃, R₂₄, V₁₁, V₁₂, V₁₃ and V₁₄has the same meaning as the aryl group represented by R₁ to R₈ and W₁ toW₄ of formula (I).

The heterocyclic group represented by R₂₁, R₂₂, R₂₃, R₂₄, V₁₁, V₁₂, V₁₃and V₄ has the same meaning as the heterocyclic group represented by R₁to R₈ and W₁ to W₄ of formula (I).

The heterocyclic ring or a condensed ring thereof represented by R₂₁,R₂₂, R₂₃, R₂₄, V₁₁, V₁₂, V₁₃ and V₁₄ is preferably a 5- or 6-memberednitrogen-containing hetero-cyclic ring (which may further form acondensed ring with other ring), provided that when R₂₁, R₂₂, R₂₃, R₂₄,V₁₁, V₁₂, V₁₃ and V₁₄ each independently forms a 6-memberednitrogen-containing heterocyclic ring (which may further form acondensed ring with other ring), the number of nitrogen atomconstituting the 6-membered nitrogen-containing heterocyclic ring is 1or 2 (the case where. the number of nitrogen atoms constituting the6-membered nitrogen-containing heterocyclic ring is 3 or more, forexample, a triazine ring, is excluded).

Examples of the heterocyclic group represented by R₂₁, R₂₂, R₂₃, R₂₄,V₁₁, V₁₂, V₁₃ and V₁₄ are the same as examples of the heterocyclic groupin formula (I), and preferred examples are also the same.

In the case where the heterocyclic group represented by R₂₁, R₂₂, R₂₃,R₂₄, V₁₁, V₁₂, V₁₃ and V₁₄ further has a substituent, examples of thesubstituent are the same as examples of the substituent in formula (I),and preferred examples are also the same.

M has the same meaning as M in formula (I), and preferred examples arealso the same.

At least one of R₂₁, R₂₂, R₂₃, R₂₄, V₁₁, V₁₂, V₁₃ and V₁₄ has an ionichydrophilic group as the substituent.

Examples of the ionic hydrophilic group and the molecular weight of thephthalocyanine compound are the same as those described above forformula (II).

The phthalocyanine compounds represented by formulae (II) and (III) eachhas at least one ionic hydrophilic group within one molecule or have atleast one ionic hydrophilic group as the substituent and therefore,exhibits good solubility or dispersibility in an aqueous medium. Fromthis viewpoint, the phthalocyanine compounds represented by formulae(II) and (III) each preferably has at least two or more ionichydrophilic groups within one molecule and at least one of the pluralityof ionic hydrophilic groups is preferably a sulfo group. In particular,a phthalocyanine compound having at least two or more sulfo groupswithin one molecule is most preferred.

The phthalocyanine compound represented by formula (II) is preferably acompound having a combination of the following (i) to (vi).

(i) Z₁ to Z₄ each independently represents a substituted orunsubstituted alkyl group, a substituted or unsubstituted cycloalkylgroup, a substituted or unsubstituted alkenyl group, a substituted orunsubstituted aralkyl group, a substituted or unsubstituted aryl group,or a substituted or unsubstituted heterocyclic group, more preferably asubstituted alkyl group, a substituted aryl group or a substitutedheterocyclic group, still more preferably a substituted alkyl group, andmost preferably an alkyl group having an ionic hydrophilic group as thesubstituent.

(ii) q₁, q₂, q₃ and q₄ each independently represents an integer of 1 or2, more preferably 2, most preferably q₁=q₂=q₃=q₄=2.

(iii) a₃₁, a₃₂, a₃₃ and a₃₄ each independently represents an integer of1 or 2, more preferably 1, most preferably a₃₁=a₃₂=a₃₃=a₃₄=1.

(iv) M is preferably Cu, Ni, Zn or Al, most preferably Cu.

(v) The molecular weight of the phthalocyanine compound is preferablyfrom 750 to 2,500, more preferably from 995 to 2,500, still morepreferably from 995 to 2,000, and most preferably from 995 to 1,800.

(vi) The phthalocyanine compound represented by formula (II) has atleast one or more ionic hydrophilic group within the molecule andtherefore, exhibits good solubility or dispersibility in an aqueousmedium. From this viewpoint, the phthalocyanine compound represented byformula (II) preferably has at least two or more ionic hydrophilicgroups within one molecule and at least one of the plurality of ionichydrophilic groups is preferably a. sulfo group. In particular, aphthalocyanine compound having at least two or more sulfo groups withinone molecule is most preferred.

As for the combination of preferred substituents in the compoundrepresented by formula (II), a compound where at least one of varioussubstituents is the preferred group is preferred, a compound where alarger number of various substituents are the preferred groups is morepreferred, and a compound where all substituents are the preferredgroups is most preferred.

The phthalocyanine compound represented by formula (III) is preferably acompound having a combination of the following (i) to (v).

(i) R₂₁, R₂₂, R₂₃ and R₂₄ each independently represents a hydrogen atom,a substituted or unsubstituted alkyl group, a substituted orunsubstituted cycloalkyl group, a substituted or unsubstituted alkenylgroup, a substituted or unsubstituted aralkyl group, a substituted orunsubstituted aryl group, or a substituted or unsubstituted heterocyclicgroup, more preferably a hydrogen atom, a substituted alkyl group, asubstituted aryl group or a substituted heterocyclic group, and mostpreferably a hydrogen atom.

(ii) V₁₁, V₁₂, V₁₃ and V₁₄ each independently represents a substitutedor unsubstituted alkyl group, a substituted or unsubstituted cycloalkylgroup, a substituted or unsubstituted alkenyl group, a substituted orunsubstituted aralkyl group, a substituted or unsubstituted aryl group,or a substituted or unsubstituted heterocyclic group, more preferably asubstituted alkyl group, a substituted aryl group or a substitutedheterocyclic group, and most preferably an alkyl group having an ionichydrophilic group as the substituent.

(iii) M is preferably Cu, Ni, Zn or Al, most preferably Cu.

(iii) The molecular weight of the phthalocyanine compound is preferablyfrom 750 to 2,500, more preferably from 995 to 2,500, still morepreferably from 995 to 2,000, and most preferably from 995 to 1,800.

(v) The phthalocyanine compound represented by formula (III) has atleast one or more ionic hydrophilic group within the molecule andtherefore, exhibits good solubility or dispersibility in an aqueousmedium. From this viewpoint, the phthalocyanine compound represented byformula (III) preferably has at least two or more ionic hydrophilicgroups within one molecule and at least one of the plurality of ionichydrophilic groups is preferably a sulfo group. In particular, aphthalocyanine compound having at least two or more sulfo groups withinone molecule is most preferred.

As for the combination of preferred substituents in the compoundrepresented by formula (III), a compound where at least one of varioussubstituents is the preferred group is preferred, a compound where alarger number of various substituents are the preferred groups is morepreferred, and a compound where all substituents are the preferredgroups is most preferred.

The phthalocyanine compound of the present invention is particularlypreferably the compound represented by formula (II) where q₁=q₂=q₃=q₄=2,namely, the substituent is a sulfonyl group.

The phthalocyanine compound represented by formula (IV) of the presentinvention is described in detail below.

Phthalocyanine derivatives conventionally used are a mixture of isomersdifferent in the site to which a specific substituent is introduced(depending on the case, the number of sites to which introduced). Thecompound (the compound represented by formula (IV); a phthalocyaninederivative having a specific structure where specific substituents eachin a specific number are selectively introduced into specific sites) ofthe present invention is a novel compound having a specific structurewhich has heretofore not been isolated and recognized. By virtue of theperformance brought out from the specific structure, this compound isvery useful as a water-soluble dye for ink jetting, imparted with highfunctionality or as an intermediate for the synthesis of thewater-soluble dye (a system comprising a mixture of isomers each havinga substituent introduced into a specific site, namely, conventionalphthalocyanine derivatives, cannot exert the objective performance ofhigh level), and can be a useful intermediate for chemical, medical oragricultural organic compounds.

Formula (IV) is described below.

Z₁, Z₂, Z₃ and Z₄ have the same meanings as Z₁, Z₂, Z₃ and Z₄ in formula(II) , and preferred examples thereof are also the same.

q₁, q₂, q₃ and q₄ each independently represents an integer of 1 or 2,preferably 2, and most preferably q₁=q₂=q₃=q₄=2.

a₃₁, a₃₂, a₃₃ and a₃₄ each independently represents an integer of 1 or2, preferably 2, and most preferably a₃₁=a₃₂=a₃₃=a₃₄=1.

M has the same meaning as M in formula (II), and preferred examplesthereof are also the same.

At least one of Z₁, Z₂, Z₃ and Z₄ has an ionic hydrophilic group as asubstituent.

Examples of the ionic hydrophilic group are the same as examples of theionic hydrophilic group in formula (II), and preferred examples thereofare also the same.

The molecular weight of the phthalocyanine compound represented byformula (IV) is preferably from 750 to 2,500, more preferably from 995to 2,500, still more preferably from 995 to 2,000, particularlypreferably from 995 to 1,800.

In general, it is known to use various phthalocyanine derivatives as anink composition for ink jetting. The phthalocyanine derivativerepresented by the following formula (V) sometimes contains an isomerwith respect to the substitution site of the substituent R_(n) (n=1 to16, R simply means a substituent and it is not intended that R_(n) allare the same substituent) (here, R₁ to R₁₆ are defined as substituentsat the 1-position to the 16-position, respectively), which inevitablyoccurs at the time of synthesis, however, these substitution siteisomers are not distinguished from each other but regarded as the samederivative in many cases. Also, in the case where the substituent Rcontains an isomer, these are not distinguished but regarded as the samephthalocyanine derivative in many cases.

The meaning that in the phthalocyanine compound of the presentinvention, the structure is different is described by referring toformula (V). With respect to the substituent R_(n) (n=1 to 16), when theconstituent atom species is different, this means that the number ofsubstituents is different or that the substitution site is different.

In the present invention, derivatives where the structure of thephthalocyanine compound represented by formula (I) is different(particularly, in the substitution site) are defined by classifyingthese into the following three types.

(1) β-Position Substitution Type:

(a phthalocyanine compound having specific substituents at the 2- and/or3-position, the 6- and/or 7-position, the 10- and/or 11-position, andthe 14- and/or 15-position)

(2) α-Position Substitution Type:

(a phthalocyanine compound having specific substituents at the 1- and/or4-position, the 5- and/or 8-position, the 9- and/or 12-position, and the13- and/or 16-position)

(3) α,β-Position Mixed Substitution Type:

(a phthalocyanine compound having specific substitutions at the 1- to16-position without any regularity)

In the present invention, phthalocyanine compound derivatives differentin the structure (particularly, in the substitution site) are describedby using these β-position substitution type, α-position substitutiontype and α,β-position mixed substitution type.

The phthalocyanine derivative for use in the present invention can besynthesized by combining the methods described or cited, for example, inShirai and Kobayashi, Phthalocyanine—Kagaku toKino—(Phthalocyanine—Chemistry and Function—), pp. 1-62, IBC, and C. C.Leznoff and A. B. P. Lever, Phthalocyanines—Properties and Applications,pp. 1-54, VCH, or methods analogous thereto.

Phthalocyanine compounds heretofore reported can be synthesized, forexample, through sulfonation, sulfonyl chloridation or amidation of anunsubstituted phthalocyanine compound as described in InternationalPatents 00/17275, 00/08103, 00/08101 and 98/41853 and JP-A-10-36471.

In this case, (1) sulfonation takes place at any site of thephthalocyanine nucleus and (2) the number of sites sulfonated isdifficult to control.

Accordingly, when a sulfo group is introduced under such reactionconditions, the site and number of sulfo groups introduced into theproduct cannot be specified and a mixture of those different in thenumber of substituents or in the substitution site inevitably results.

If a phthalocyanine compound is synthesized starting from such aproduct, the compound is obtained as a mixture containing several kindsof compounds different in the number of substituents or in thesubstitution site because the number of sulfamoyl groups substituted ortheir substitution sites cannot be specified.

On the other hand, out of the phthalocyanine compounds represented byformulae (I) to (IV) of the present invention, for example, thephthalocyanine compound represented by formula (X) can be synthesized byreacting a phthalonitrile derivative represented by the followingformula (VI) and/or a diiminoisoindoline derivative represented by thefollowing formula (VII) with a metal derivative represented by thefollowing formula (VIII).

Also, the phthalocyanine compound represented by formula (III) of thepresent invention can be synthesized by reacting a sodium4-sulfophthalate represented by formula (IX) and a metal derivativerepresented by formula (VIII) to obtain phthalocyaninecopper(II)-tetrasodium tetrasulfonate, deriving a corresponding sulfonylchloride therefrom and reacting it with an objective amine or anilinederivative (for example, when W₁, W₂, W₃ and W₄ are W₁: {—SO₂N (R₂₁)(V₁₁)}, W₂: {—SO₂N (R₂₂) (V₁₂)}, W₃: {—SO₂N (R₂₃) (V₁₃} and W₄:{—SO₂N(R₂₄) (V₁₄) }).

In formula (VI) and/or formula (VII), t has the same meaning as 1, m, nand p in formula (I). In formula (X), W₁, W₂, W₃ and W₄ eachindependently represents W₁: {—S(O)q₁-Z₁}, W₂: {—S(O)q₂-Z₂), W₃:{—S(O)q₃-Z₃} and W₄: {—S(O)q₄-Z₄} in formula (II), and/or W₁:{—SO₂N(R₂₁) (V₁₁)}, W₂: {—SO₂N(R₂₂) (V₁₂) } , W₃: {—SO₂N(R₂₃) (V₁₃)} andW₄: {—SO₂N(R₂₄) (V₁4) } in formula (III).

Formula (VIII):M-(Y)_(d)wherein M has the same meaning as M in formulae (I) to (IV), Yrepresents a monovalent or divalent ligand such as halogen atom, acetateanion, acetyl acetonate and oxygen, and d represents an integer of 1 to4.

Examples of the metal derivative represented by formula (VIII) include ahalide, a carboxylic acid derivative, a sulfate, a nitrate, a carbonylcompound, an oxide and a complex of Al, Si, Ti, V, Mn, Fe, Co, Ni, Cu,Zn, Ge, Ru, Rh, Pd, In, Sn, Pt and Pb. Specific examples thereof includecopper chloride, copper bromide, copper iodide, nickel chloride, nickelbromide, nickel acetate, cobalt chloride, cobalt bromide, cobaltacetate, iron chloride, zinc chloride, zinc bromide, zinc iodide, zincacetate, vanadium chloride, vanadium oxytrichloride, palladium chloride,palladium acetate, aluminum chloride, manganese chloride, manganeseacetate, acetylacetone manganese, lead chloride, lead acetate, indiumchloride, titanium chloride and tin chloride.

The amounts of the metal derivative and the phthalonitrile compoundrepresented by formula (VI) used are preferably, in terms of the molarratio, from 1:3 to 1:6.

The amounts of the metal derivative and the diiminoisoindolinederivative represented by formula (VII) are preferably, in terms of themolar ratio, from 1:3 to 1:6.

The reaction is usually performed in the presence of a solvent. For thesolvent, an organic solvent having a boiling point of 80° C. or more,preferably 130° C. or more is used. Examples thereof include n-amylalcohol, n-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol,2-heptanol, 1-octanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol,propylene glycol, ethoxyethanol, propoxyethanol, butoxyethanol,dimethylaminoethanol, diethylaminoethanol, trichlorobenzene,chloronaphthalene, sulfolane, nitrobenzene, quinoline and urea. Theamount of the solvent used is from 1 to 100 times in mass (i.e., inweight), preferably from 5 to 20 times in mass, the phthalonitrile.compound.

In the reaction, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) or ammoniummolybdate may be added as the catalyst. The amount thereof added is from0.1 to 10 molar times, preferably from 0.5 to 2 molar times per 1 mol ofthe phthalonitrile compound and/or diiminoisoindoline derivative.

The reaction temperature is from 80 to 300° C., preferably from 100 to250° C., more preferably from 130 to 230° C. If the reaction temperatureis less than 80° C., the reaction rate is extremely low, whereas if itexceeds 300° C., decomposition of the phthalocyanine compound may occur.

The reaction time is from 2 to 20 hours, preferably from 5 to 15 hours,more preferably from 5 to 10 hours. If the reaction time is less than 2hours, unreacted raw materials remain in a large amount, whereas if itexceeds 20 hours, decomposition of the phthalocyanine compound mayoccur.

The product obtained by this reaction is treated according to the normalafter-treating method in the organic synthesis reaction and then throughor not though purification, used as a commercial product.

The after-treatment must be a treatment of giving lithium ion as thecounter cation of the ionic hydrophilic group.

More specifically, for example, the product isolated from the reactionsystem can be provided as a commercial product without purifying it orafter performing operations of recrystallization and purificationindividually or in combination, for example, by column chromatography(for example, gel permeation chromatography (SEPHADEX™ LH-20, producedby Pharmacia)).

Also, after the completion of reaction, the reaction solvent is removedor not removed by distillation, the product is charged in water or iceand then neutralized or not neutralized, and the product isolated can beprovided as a commercial product without purifying it or afterperforming operations of recrystallization and purification individuallyor in combination, for example, by column chromatography.

Furthermore, after the completion of reaction, the reaction solvent isremoved or not removed by distillation, the product is charged in wateror ice, neutralized or not neutralized, and then extracted with anorganic solvent/an aqueous solution, and the product extracted can beprovided as a commercial product without purifying it or afterperforming operations of recrystallization and purification individuallyor in combination by column chromatography.

The thus-obtained phthalocyanine compound represented by formulae (I),(II), (III) and (IV) usually includes the compounds represented by thefollowing formulae (a)-1 to (a)-4. These four compounds are isomersdifferent in the substitution sites of G₁ to G₄.

The compounds represented by formulae (a)-1 to (a)-4 are a β-positionsubstitution type compound (a phthalocyanine compound having specificsubstituents at the 2- and/or 3-position, the 6- and/or 7-position, the10- and/or 11-position, and the 14- and/or 15-position) and utterlydifferent in the structure (substitution site) from the α-positionsubstitution type and the α,β-position mixed substitution type. Thisstructural feature is very important for the improvement of fastness.

In any substitution type, the specific substituents represented by, forexample, W₁, W₂, W₃ and W₄ in formula (I) are very important for theimprovement of fastness.

Furthermore, the structural feature very important for the improvementof fastness is a compound where specific substituents (W₁, W₂, W₃, W₄)in a specific number are introduced into specific sites (β-positionsubstitution type) of a phthalocyanine mother nucleus {for example, inthe case of a phthalocyanine mother nucleus, at least one or more ofthose specific substituents are contained in each pair of (2-positionand/or 3-position), (6-position and/or 7-position), (10-position and/or11-position) and (14-position and/or 15-position)}.

As for the structural feature of a water-soluble phthalocyanine compoundhaving a specific spectral absorption property (absorbance ratiob/a<0.8; promotion of aggregated state), it has been found that acompound where specific substituents (W₁, W₂, W₃ and W₄, particularly,these are an electron-withdrawing group, preferably a sulfamoyl group ora sulfonyl group) in a specific number are introduced into specificsites (β-position substitution type) of a phthalocyanine mother nucleusis a most preferred structure in view of fastness and (color) hue of theimage because the aggregated state is promoted.

In the present invention, it has been found that when the counter cationof the ionic hydrophilic group is lithium ion, the solubility in waterand a water-miscible organic solvent is remarkably improved as comparedwith other cation species. Also in the phthalocyanine compoundsatisfying the spectral absorption property of the present invention andpromoted in the formation of aggregated state, when the counter cationis lithium ion, the bronze phenomenon can be prevented from occurring onthe recording material surface without changing the spectral absorptionproperty and without impairing fastness and (color) hue of the image.

The ozone gas resistance referred to in the present invention isrepresented by a resistance against ozone gas and includes resistance(fastness) against oxidative atmospheres other than ozone gas. That is,the phthalocyanine compound represented by formula (I) according to thepresent invention is characterized by the strong resistance againstoxidative gases present in the general environment, such as nitrogenoxide mostly contained in exhaust gas of automobiles, sulfur oxidemostly contained in exhaust from thermal power stations or factories,ozone gas generated by a radical chain reaction of these gasesphotochemically caused with solar light, photochemical smog abundant inoxygen-nitrogen or oxygen-hydrogen radical, and hydrogen peroxideradical generated from sites using special chemicals, for example, hairsaloon. Accordingly, in the case where the image life is limited by theoxidative deterioration of image, such as outdoor advertisement andguide in railroad facility, ozone gas resistance can be improved byusing the phthalocyanine compound of the present invention as theimage-forming material.

Specific examples of the phthalocyanine compound represented by formula(I) of the present invention are set forth in the following tables(Compounds 101 to 215), however, the phthalocyanine compound of thepresent invention is not limited thereto.

In Tables, specific examples of each pair of (R₁R₄), (R₂R₃) , (R₅R₈) ,(R₆R₇) , (R₉R₁₂) , (R₁₀R₁₁) , (R₁₃R₁₆) and (R₁₄R₁₅) are independentlyshown in an irregular order. TABLE 1 Compound M R₁R₄ R₂R₃ R₅R₈ R₆R₇ 101Cu H, H, H, H, H —SO—(CH₂)₃SO₃Li H —SO—(CH₂)₃SO₃Li 102 Cu H, H, H, H, H—SO₂ —(CH₂)₃SO₃Li H —SO₂—(CH₂)₃SO₃Li 103 Cu H, H, H, H, H

H

104 Cu H, H, H, H, H

H

105 Cu H, —SO—(CH₂)₃SO₃Li, H, —SO—(CH₂)₃SO₃Li, H —SO—(CH₂)₃SO₃Li H—SO—(CH₂)₃SO₃Li Compound R₉R₁₂ R₁₀R₁₁ R₁₃R₁₆ R₁₄R₁₅ 101 H, H, H, H, H—SO—(CH₂)₃SO₃Li H —SO—(CH₂)₃SO₃Li 102 H, H, H, H, H, —SO₂—(CH₂)₃SO₃Li H—SO₂—(CH₂)₃SO₃Li 103 H, H, H, H, H

H

104 H, H, H, H, H

H

105 H, —SO—(CH₂)₃SO₃Li, H, —SO—(CH₂)₃SO₃Li H —SO—(CH₂)₃SO₃Li H—SO—(CH₂)₃SO₃Li

TABLE 2 Compound M R₁R₄ R₂R₃ R₅R₈ R₆R₇ 106 Cu H, —SO₂—(CH₂)₃SO₃Li H—SO₂—(CH₂)₃SO₃Li H —SO₂—(CH₂)₃SO₃Li H —SO₂—(CH₂)₃SO₃Li 107 Cu H, H, H,H, H

H

108 Cu H, H, H, H, H

H

109 Cu H, H, H, H, H

H

110 Cu H, H, H, H, H

H

Compound R₉R₁₂ R₁₀R₁₁ R₁₃R₁₆ R₁₄R₁₅ 106 H, —SO₂—(CH₂)₃SO₃Li H—SO₂—(CH₂)₃SO₃Li H —SO₂—(CH₂)₃SO₃Li H —SO₂—(CH₂)₃SO₃Li 107 H, H, H, H, H

H

108 H, H, H, H, H

H

109 H, H, H, H, H

H

110 H, H, H, H, H

H

TABLE 3 Compound M R₁R₄ R₂R₃ R₅R₈ R₆R₇ 111 Cu H, H, H, H, H

H

112 Cu H, H, H, H, H

H

113 Cu H, H, H, H, H

H

114 Cu H, H, H, H, H

H

115 Cu H, H, H, H, H

H

Compound R₉R₁₂ R₁₀R₁₁ R₁₃R₁₆ R₁₄R₁₅ 111 H, H, H, H, H

H

112 H, H, H, H, H

H

113 H, H, H, H, H

H

114 H, H, H, H, H

H

115 H, H, H, H, H

H

TABLE 4 Compound M R₁R₄ R₂R₃ R₅R₈ R₆R₇ 116 Cu H, H, H, H, H

H

117 Cu H, H, H, H, H

H

118 Cu H, H, H, H, H

H

119 Cu H, H, H, H, H

H

120 Cu H, H, H, H, H

H

Compound R₉R₁₂ R₁₀R₁₁ R₁₃R₁₆ R₁₄R₁₅ 116 H, H, H, H, H

H

117 H, H, H, H, H

H

118 H, H, H, H, H

H

119 H, H, H, H, H

H

120 H, H, H, H, H

H

TABLE 5 Compound M R₁R₄ R₂R₃ R₅R₈ R₆R₇ 121 Cu H, H, H, H, H

H

122 Cu H, H, H, H, H

H

123 Cu H, H, H, H, H

H

124 Cu H, H, H, H, H

H

125 Cu H, H, H, H, H

H

Compound R₉R₁₂ R₁₀R₁₁ R₁₃R₁₆ R₁₄R₁₅ 121 H, H, H, H, H

H

122 H, H, H, H, H

H

123 H, H, H, H, H

H

124 H, H, H, H, H

H

125 H, H, H, H, H

H

TABLE 6 Com- pound M R₁R₄ R₂R₃ R₅R₈ R₆R₇ 126 Cu H, H, H, H, H

H

127 Cu H, H, H, H, H

H

128 Cu H, H, H, H, H

H

129 Cu H, H, H, H, H

H

130 Cu H, H, H, H, H

H

Com- pound R₁R₄ R₂R₃ R₅R₈ R₆R₇ 126 H, H, H, H, H

H

127 H, H, H, H, H

H

128 H, H, H, H, H

H

129 H, H, H, H, H

H

130 H, H, H, H, H

H

TABLE 7 Compound M R₁ R₄ R₂ R₃ R₅ R₈ R₆ R₇ R₉ R₁₂ R₁₀ R₁₁ R₁₃ R₁₆ R₁₄R₁₅ 131 Cu H, H —Cl, H, H —Cl, H, H —Cl, H, H —Cl, —SO₂—(CH₂)₃SO₃Li,—SO₂—(CH₂)₃SO₃Li —SO₂—(CH₂)₃SO₃Li —SO₂—(CH₂)₃SO₃Li 132 Cu H, H —OCH₃, H,H —OCH₃, H, H —OCH₃, H, H —OCH₃, —SO—(CH₂)₃SO₃Li —SO—(CH₂)₃SO₃Li—SO—(CH₂)₃SO₃Li —SO—(CH₂)₃SO₃Li 133 Cu H, H —CN, H, H —CN, H, H —CN, H,H —CN, —SO₂—(CH₂)₄SO₃Li —SO₂—(CH₂)₄SO₃Li —SO₂—(CH₂)₄SO₃Li—SO₂—(CH₂)₄SO₃Li 134 Ni H, H —SO₂—(CH₂)₃SO₃Li, H, H —SO₂—(CH₂)₃SO₃Li, H,H —SO₂—(CH₂)₃SO₃Li, H, H —SO₂—(CH₂)₃SO₃Li, —SO₂—(CH₂)₃SO₃Li—SO₂—(CH₂)₃SO₃Li —SO₂—(CH₂)₃SO₃Li —SO₂—(CH₂)₃SO₃Li 135 Zn H, H H, H, HH, H, H H, H, H H, —SO₂—(CH₂)₃SO₃Li —SO₂—(CH₂)₃SO₃Li —SO₂—(CH₂)₃SO₃Li—SO₂—(CH₂)₃SO₃Li

TABLE 8 Compound M R₁R₄ R₂R₃ R₅R₈ R₆R₇ 136 Cu H, H, H, H, H

H

137 Cu H, H, H, H, H

H

138 Cu H, H, H, H, H

H

139 Cu H, H, H, H, H

H

140 Cu H, H, H, H, H

H

141 Cu H, H, H, H, H

H

142 Cu H, H, H, H, H

H

143 Cu H, H, H, H, H

H

144 Cu H, H, H, H, H

H

145 Cu H, H, H, H, H

H

Compound R₉R₁₂ R₁₀R₁₁ R₁₃R₁₆ R₁₄R₁₅ 136 H, H, H, H, H

H

137 H, H, H, H, H

H

138 H, H, H, H, H

H

139 H, H, H, H, H

H

140 H, H, H, H, H

H

141 H, H, H, H, H

H

142 H, H, H, H, H

H

143 H, H, H, H, H

H

144 H, H, H, H, H

H

145 H, H, H, H, H

H

TABLE 9 Com- pound M R₁R₄ R₂R₃ R₅R₈ R₆R₇ 146 Cu H, H, H, H, H

H

147 Cu H, H, H, H, H

H

148 Cu H, H, H, H, H

H

149 Cu H, H, H, H, H

H

150 Cu H, H, H, H, H

H

151 Cu H, H, H, H, H

H

152 Cu H, H, H, H, H

H

153 Cu H, H, H, H, H

H

154 Cu H, H, H, H, H

H

155 Cu H, H, H, H, H

H

Com- pound R₁R₄ R₂R₃ R₅R₈ R₆R₇ 146 H, H, H, H, H

H

147 H, H, H, H, H

H

148 H, H, H, H, H

H

149 H, H, H, H, H

H

150 H, H, H, H, H

H

151 H, H, H, H, H

H

152 H, H, H, H, H

H

153 H, H, H, H, H

H

154 H, H, H, H, H

H

155 H, H, H, H, H

H

TABLE 10 Compound M R₁R₄ R₂R₃ R₅R₈ R₆R₇ 156 Cu H, H, H, H, H

H

157 Cu H, H, H, H, H

H

158 Cu H, H, H, H, H

H

159 Cu H, H, H, H, H

H

160 Cu H, H, H, H, H

H

161 Cu H, H, H, H, H

H

162 Cu H, H, H, H, H

H

163 Cu H, H, H, H, H

H

164 Cu H, H, H, H, H

H

165 Cu H, H, H, H, H

H

Compound R₉R₁₂ R₁₀R₁₁ R₁₃R₁₆ R₁₄R₁₅ 156 H, H, H, H, H

H

157 H, H, H, H, H

H

158 H, H, H, H, H

H

159 H, H, H, H, H

H

160 H, H, H, H, H

H

161 H, H, H, H, H

H

162 H, H, H, H, H

H

163 H, H, H, H, H

H

164 H, H, H, H, H

H

165 H, H, H, H, H

H

TABLE 11 Compound M R₁R₄ R₂R₃ R₅R₈ R₆R₇ 166 Cu H, H, H, H, H

H

167 Cu H, H, H, H, H

H

168 Cu H, H, H, H, H

H

169 Cu H, H, H, H, H

H

170 Cu H, H, H, H, H

H

Compound R₉R₁₂ R₁₀R₁₁ R₁₃R₁₆ R₁₄R₁₅ 166 H, H, H, H, H

H

167 H, H, H, H, H

H

168 H, H, H, H, H

H

169 H, H, H, H, H

H

170 H, H, H, H, H

H

TABLE 12 Com- pound M R₁R₄ R₂R₃ R₅R₈ R₆R₇ 171 Cu H, H, H, H, H—SO₂(CH₂)₂O(CH₂)₂SO₃Li H —SO₂(CH₂)₂O(CH₂)₂SO₃Li 172 Cu H, H, H, H, H

H

173 Cu H, H, H, H, H —SO₂[(CH₂)₂O]₂(CH₂)₂SO₃Li H—SO₂[(CH₂)₂O]₂(CH₂)₂SO₃Li 174 Cu H, H, H, H, H —SO₂[(CH₂)₂O]₃(CH₂)₂SO₃LiH —SO₂[(CH₂)₂O]₃(CH₂)₂SO₃Li 175 Cu H, H, H, H, H

H

Com- pound R₉R₁₂ R₁₀R₁₁ R₁₃R₁₆ R₁₄R₁₅ 171 H, H, H, H, H—SO₂(CH₂)₂O(CH₂)₂SO₃Li H —SO₂(CH₂)₂O(CH₂)₂SO₃Li 172 H, H, H, H, H

H

173 H, H, H, H, H —SO₂[(CH₂)₂O]₂(CH₂)₂SO₃Li H —SO₂[(CH₂)₂O]₂(CH₂)₂SO₃Li174 H, H, H, H, H —SO₂[(CH₂)₂O]₃(CH₂)₂SO₃Li H —SO₂[(CH₂)₂O]₃(CH₂)₂SO₃Li175 H, H, H, H,

H

TABLE 13 Compound M R₁R₄ R₂R₃ R₅R₈ R₆R₇ 176 Zn H, H, H, H, H

H

177 Cu H, H, H, H, H

H

178 Cu H, H, H, H, H

H

179 Cu H, H, H, H, H

H

180 Cu H, H, H, H, H —SO₂NH.(CH₂)₃—SO₃Li H —SO₂NH.(CH₂)₃—SO₃Li CompoundR₉R₁₂ R₁₀R₁₁ R₁₃R₁₆ R₁₄R₁₅ 176 H, H, H, H, H

H

177 H, H, H, H, H

H

178 H, H, H, H, H

H

179 H, H, H, H, H

H

180 H, H, H, H, H —SO₂NH.(CH₂)₃—SO₃Li H —SO₂NH.(CH₂)₃—SO₃Li

TABLE 14 Compound M R₁R₄ R₂R₃ R₅R₈ R₆R₇ 181 Cu H, H, H, H, H

H

182 Cu H, H, H, H, H

H

183 Ni H, H, H, H, H

H

184 Cu H, H, H, H, H

H

185 Zn H, H, H, H, H

H

Compound R₉R₁₂ R₁₀R₁₁ R₁₃R₁₆ R₁₄R₁₅ 181 H, H, H, H, H

H

182 H, H, H, H, H

H

183 H, H, H, H, H

H

184 H, H, H, H, H

H

185 H, H, H, H, H

H

TABLE 15 Compound M R₁R₄ R₂R₃ R₅R₈ R₆R₇ 186 Cu H, H, H, H, H

H

187 Cu H, H, H, H, H

H

188 Cu H, H, H, H, H

H

189 Cu H, H, H, H, H

H

190 Cu H, H, H, H, H

H

Compound R₉R₁₂ R₁₀R₁₁ R₁₃R₁₆ R₁₄R₁₅ 186 H, H, H, H, H

H

187 H, H, H, H, H

H

188 H, H, H, H, H

H

189 H, H, H, H, H

H

190 H, H, H, H, H

H

TABLE 16 Compound M R₁R₄ R₂R₃ R₅R₈ R₆R₇ 191 Cu H, H, H, H, H

H

192 Cu H, H, H, H, H

H

193 Cu H, H, H, H, H

H

194 Cu H, H, H, H, H

H

195 Cu H, H, H, H, H

H

Compound R₉R₁₂ R₁₀R₁₁ R₁₃R₁₆ R₁₄R₁₅ 191 H, H, H, H, H

H

192 H, H, H, H, H

H

193 H, H, H, H, H

H

194 H, H, H, H, H

H

195 H, H, H, H, H

H

TABLE 17 Compound M R₁R₄ R₂R₃ R₅R₈ R₆R₇ 196 Cu H, H, H, H, H

H

197 Cu H, H, H, H, H

H

198 Cu H, H, H, H, H

H

199 Cu H, H, H, H, H

H

200 Cu H, H, H, H, H

H

Compound R₉R₁₂ R₁₀R₁₁ R₁₃R₁₆ R₁₄R₁₅ 196 H, H, H, H, H

H

197 H, H, H, H, H

H

198 H, H, H, H, H

H

199 H, H, H, H, H

H

200 H, H, H, H, H

H

TABLE 18 Compound M R₁R₄ R₂R₃ R₅R₈ R₆R₇ 201 Cu H, H, H, H, H

H

202 Cu H, H, H, H, H

H

203 Cu H, H, H, H, H

H

204 Cu H, H, H, H, H

H

205 Cu H, H, H, H, H

H

Compound R₉R₁₂ R₁₀R₁₁ R₁₃R₁₆ R₁₄R₁₅ 201 H, H, H, H, H

H

202 H, H, H, H, H

H

203 H, H, H, H, H

H

204 H, H, H, H, H

H

205 H, H, H, H, H

H

TABLE 19 Compound M R₁R₄ R₂R₃ R₅R₈ R₆R₇ 206 Cu H, H, H, H, Cl

Cl

207 Cu H, H, H, H, SCH₃

SCH₃

208 Cu H, H, H, H, Cl

Cl

209 Ni H, H, H, H, H

H

210 Zn H, H, H, H, H

H

Compound R₉R₁₂ R₁₀R₁₁ R₁₃R₁₆ R₁₄R₁₅ 206 H, H, H, H, Cl

Cl

207 H, H, H, H, SCH₃

SCH₃

208 H, H, H, H, Cl

Cl

209 H, H, H, H, H

H

210 H, H, H, H, H

H

TABLE 20 Compound M R₁R₄ R₂R₃ R₅R₈ R₆R₇ 211 Cu H, H, H, H, H

HJ

212 Cu H, H, H, H, H

H

213 Cu H, H, H, H, H

H

214 Cu H, H, H, H, H

H

215 Cu H, H, H, H, H

H

Compound R₉R₁₂ R₁₀R₁₁ R₁₃R₁₆ R₁₄R₁₅ 211 H, H, H, H, H

HJ

212 H, H, H, H, H

H

213 H, H, H, H, H

H

214 H, H, H, H, H

H

215 H, H, H, H, H

H

Examples of the use of the phthalocyanine compound of the presentinvention include a material for forming an image, particularly a colorimage. Specific examples thereof include an ink jet recording materialwhich is described in detail later, a heat-sensitive transfer-type imagerecording material, a pressure-sensitive recording material, a recordingmaterial using the electro-photographic system, a transfer-type silverhalide light-sensitive material, a printing ink and a recording pen.Among these, preferred are an ink jet recording material, aheat-sensitive transfer-type image recording material and a recordingmaterial using the electrophotographic system, more preferred is an inkjet recording material. The phthalocyanine compound of the presentinvention can also be applied to a dyeing solution for dyeing variousfibers of color filter used in solid image camera element such as LCDand CCD described in U.S. Pat. No. 4,808,501 and JP-A-6-35182.

The compound of the present invention can be adjusted to have physicalproperties suitable for use, such as solubility and heat transfer, bythe substituent. Furthermore, the compound of the present invention canbe used in a uniformly dissolved state, a dispersed and dissolved statesuch as emulsification dispersion, or a solid dispersion state accordingto the system where the compound is used.

The ink for ink jetting comprising the ink of the present invention isdescribed below. The ink for ink jetting can be produced by dissolvingand/or dispersing the above-described phthalocyanine compound in alipophilic or aqueous medium. Preferably, an aqueous medium is used. Ifdesired, other additives are contained within the range of not impairingthe effect of the present invention. Examples of other additives includeknown additives such as drying inhibitor (wetting agent), discolorationinhibitor, emulsification stabilizer, permeation accelerator,ultraviolet absorbent, antiseptic, fungicide, pH adjusting agent,surface tension adjusting agent, defoaming agent, viscosity controllingagent, dispersant, dispersion stabilizer, rust inhibitor and chelatingagent. These various additives are directly added to the ink solution inthe case of a water-soluble ink. When an oil-soluble dye is used in theform of a dispersion, the additives are generally added to thedispersion after the preparation of a dye dispersion, but may be addedto the oil or aqueous phase at the preparation.

The drying inhibitor is suitably used for the purpose of preventingoccurrence of clogging due to drying of the ink for ink jetting at theink jetting port of a nozzle used for the ink jet recording system.

The drying inhibitor is preferably a water-soluble organic solventhaving a vapor pressure lower than water. Specific examples thereofinclude polyhydric alcohols represented by ethylene glycol, propyleneglycol, diethylene glycol, polyethylene glycol, thiodiglycol,dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetyleneglycol derivative, glycerin and trimethylol-propane; lower alkyl ethersof polyhydric alcohol, such as ethylene glycol monomethyl(or ethyl)ether, diethylene glycol monomethyl(or ethyl) ether and triethyleneglycol monoethyl(or butyl) ether; heterocyclic rings such as2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinoneand N-ethylmorpholine; sulfur-containing compounds such as sulfolane,dimethylsulfoxide and 3-sulfolene; polyfunctional compounds such asdiacetone alcohol and diethanolamine; and urea derivatives. Among these,polyhydric alcohols such as glycerin and diethylene glycol arepreferred. These drying inhibitors may be used individually or incombination of two or more thereof. The drying inhibitor is preferablycontained in the ink in an amount of 10 to 50 wt %.

The permeation accelerator is suitably used for the purpose of obtaininggood permeation of the ink for ink jetting into paper. Examples of thepermeation accelerator which can be used include alcohols such asethanol, isopropanol, butanol, di(tri)ethylene glycol monobutyl etherand 1,2-hexanediol, sodium laurylsulfate, sodium oleate and nonionicsurfactants. A sufficiently high effect can be obtained by adding from 5to 30 wt % of the permeation accelerator to the ink. The permeationaccelerator is preferably used within the amount range of causing noblurring of printed letter or no print through.

The ultraviolet absorbent is used for the purpose of improving thestorability of image. Examples of the ultraviolet absorbent which can beused include benzotriazole-base compounds described in JP-A-58-185677,JP-A-61-190537, JP-A-2-782, JP-A-5-197075 and JP-A-9-34057,benzophenone-base compounds described in JP-A-46-2784, JP-A-5-194483 andU.S. Pat. No. 3,214,463, cinnamic acid-base compounds described inJP-B-48-30492, JP-B-56-21141 and JP-A-10-88106, triazine-base compoundsdescribed in JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621and Japanese Unexamined Published International Application 8-501291,compounds described in Research Disclosure No. 24239, and compounds ofabsorbing ultraviolet light and emitting fluorescent light, so-calledfluorescent brightening agents represented by stilbene-base compound andbenzoxazole-base compound.

The discoloration inhibitor is used for the purpose of improving thestorability of image. Examples of the discoloration inhibitor which canbe used include various organic discoloration inhibitors and metalcomplex-base discoloration inhibitors. Examples of the organicdiscoloration inhibitor include hydroquinones, alkoxy-phenols,dialkoxyphenols, phenols, anilines, amines, indanes, chromans,alkoxyanilines and heterocyclic rings. Examples of the metal complexinclude nickel complex and zinc complex. More specifically, compoundsdescribed in patents cited in Research Disclosure, Nos. 17643 (ItemsVII-I to VII-J), 15162, 18716 (page 650, left column) 36544 (page 527),307105 (page 872) and 15162, and compounds included in formulae ofrepresentative compounds and in exemplary compounds described inJP-A-62-215272 (pages 127 to 137) can be used.

Examples of the fungicide include sodium dehydro-acetate, sodiumbenzoate, sodium pyridinethione-l-oxide, ethyl p-hydroxybenzate,1,2-benzisothiazolin-3-one and salts thereof. The fungicide ispreferably used in the ink in an amount of 0.02 to 1.00 wt %.

As the pH adjusting agent, the above-described neutralizer (e.g.,organic base, inorganic alkali) can be used. The pH adjusting agent isused for the purpose of improving the storage stability of the ink forink jetting and is preferably added to adjust the ink for ink jetting toa pH of 6 to 10, more preferably to a pH of 7 to 10.

The surface tension adjusting agent includes nonionic, cationic andanionic surfactants. Here, the surface tension of the ink for inkjetting of the present invention is preferably from 25 to 70 mN/m, morepreferably from 25 to 60 mN/m. Also, the viscosity of the ink for inkjetting of the present invention is preferably 30 mPas or less, morepreferably 20 mPa·s or less. Preferred examples of the surfactantinclude anionic surfactants such as fatty acid salt, alkylsulfuric acidester salt, alkylbenzenesulfonate, alkylnaphthalenesulfonate,dialkylsulfosuccinate, alkylphosphoric acid ester salt,naphthalenesulfonic acid formalin condensate andpolyoxyethylenealkylsulfuric acid ester salt, and nonionic surfactantssuch as polyoxyethylene alkyl ether, polyoxyethylene alkylallyl ether,polyoxyethylene fatty acid ester, sorbitan fatty acid ester,polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine,glycerin fatty acid ester and oxyethylene oxypropylene block copolymer.Also, SURFYNOLS (produced by Air Products & Chemicals), which is anacetylene-base polyoxyethylene oxide surfactant, is preferably used. Inaddition, amine oxide-type amphoteric surfactants such asN,N-dimethyl-N-alkylamine oxide are preferred. Furthermore, surfactantsdescribed in JP-A-59-157636 (pages (37) to (38)) and ResearchDisclosure, No. 308119 (1989) can be used.

As the defoaming agent, for example, a chelating agent represented bythe fluorine- or silicon-containing compound and EDTA can also be used,if desired.

In the case of dispersing the phthalocyanine compound of the presentinvention in an aqueous medium, a colored fine particle containing thedye and an oil-soluble polymer is preferably dispersed in an aqueousmedium as described in JP-A-11-286637, JP-A-2001-240763,JP-A-2001-262039 and JP-A-2001-247788 or the phthalocyanine compound ofthe present invention dissolved in a high boiling point organic solventis preferably dispersed in an aqueous medium as described inJP-A-2001-262018, JP-A-2001-240763, JP-A-2001-335734 andJP-A-2002-80772. With respect to the specific method for dispersing thephthalocyanine compound of the present invention in an aqueous medium,the oil-soluble polymer, high boiling point organic solvent andadditives used, and the amounts thereof, those described in the abovepatent publications can be preferably used. Also, the azo compound,which is solid, can be dispersed as it is in a fine particle state. Atthe dispersion, a dispersant or a surfactant can be used. As for thedispersing device, a simple stirrer, an impeller stirring system, anin-line stirring system, a mill system (e.g., colloid mill, ball mill,sand mill, attritor, roll mill, agitator mill), an ultrasonic wavesystem and a high-pressure emulsification dispersion system(high-pressure homogenizer and as the commercially available device,specific examples thereof include Gaulin Homogenizer, Microfluidizer andDeBEE 2000) can be used. The preparation method of the ink for inkjetting is described in detail, in addition to the above patentpublications, in JP-A-5-148436, JP-A-5-295312, JP-A-7-97541,JP-A-7-82515, JP-A-7-118584, JP-A-11-286637 and JP-A-2001-271003 and thecontents described in these patent publications can be used also for thepreparation of the ink for ink jetting of the present invention.

As the aqueous medium, a mixture comprising water as the main componentand a water-miscible organic solvent added, if desired, can be used.Examples of the water-miscible organic solvent include alcohols (e.g.,methanol, ethanol, propanol, isopropanol, butanol, isobutanol,sec-butanol, tert-butanol, pentanol, hexanol, cyclohexanol, benzylalcohol), polyhydric alcohols (e.g., ethylene glycol, diethylene glycol,triethylene glycol, polyethylene glycol, propylene glycol, dipropyleneglycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol,glycerin, hexanetriol, thiodiglycol), glycol derivatives (e.g., ethyleneglycol monomethyl ether, ethylene glycol monoethyl ether, ethyleneglycol monobutyl ether, diethylene glycol, monomethyl ether, diethyleneglycol monobutyl ether, propylene glycol monomethyl ether, propyleneglycol monobutyl ether, dipropylene glycol monomethyl ether, triethyleneglycol monomethyl ether, ethylene glycol diacetate, ethylene glycolmonomethyl ether acetate, triethylene glycol monomethyl ether,triethylene glycol, monoethyl ether, ethylene glycol monophenyl ether),amines (e.g., ethanolamine, diethanolamine, triethanolamine,N-methyldiethanolamine, N-ethyldiethanolamine, morpholine,N-ethylmorpholine, ethylenediamine, diethylenetriamine,triethylenetetramine, polyethyleneimine, tetramethyl-propylenediamine)and other polar solvents (e.g., formamide, N,N-dimethylformamide,N,N-dimethylacetoamide, dimethylsulfoxide, sulfolane, 2-pyrrolidone,N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone,1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). Thesewater-miscible organic solvents can be used in combination of two ormore thereof.

In 100 parts by weight of the ink or ink for ink jetting of the presentinvention, from 0.2 to 10 parts by weight of the phthalocyanine compoundis preferably contained. Furthermore, in the ink for ink jetting of thepresent invention, other coloring agent may be used in combination withthe phthalocyanine compound. In the case of using two or more coloringagents in combination, the total content of the coloring agents ispreferably in the above-described range.

The ink for ink jetting of the present invention can be used not onlyfor the formation of a monochromatic image but also for the formation ofa full color image. For forming a full color image, a magenta color toneink, a cyan color tone ink and a yellow color tone ink can be used.Also, for adjusting the color tone, a black color tone ink may befurther used. In these inks, other coloring material (dye or pigment)may also be used in addition to the phthalocyanine compound of thepresent invention so as to improve the image reproducing performance.

The yellow dye which can be used together with the phthalocyaninecompound of the present invention may be any yellow dye. Examplesthereof include aryl- or heteryl-azo dyes having a phenol, a naphthol,an aniline, a hetero-cyclic ring (e.g., pyrazolone, pyridone), an openchain-type active methylene compound or the like as the couplingcomponent (hereinafter referred to as “coupler component”); azomethinedyes having an open chain-type active methylene compound or the like asthe coupler component; methine dyes such as benzylidene dye andmonomethine oxonol dye; and quinone-base dyes such as naphthoquinone dyeand anthraquinone dye. Other examples of the dye species includequinophthalone dye, nitro-nitroso dye, acridine dye and acridinone dye.

The magenta dye which can be used may be any magenta dye. Examplesthereof include aryl- or heteryl-azo dyes having a phenol, a naphthol oran aniline as the coupler component; azomethine dyes having a pyrazoloneor a pyrazolotriazole as the coupler component; methine dyes such asarylidene dye, styryl dye, merocyanine dye, cyanine dye and oxonol dye;carbonium dyes such as diphenylmethane dye, triphenylmethane dye andxanthene dye; quinone dyes such as naphthoquinone, anthraquinone andanthrapyridone; and condensed polycyclic dyes such as dioxazine dye.

The cyan dye which can be used may be any cyan dye. Examples thereofinclude aryl- or heteryl-azo dyes having a phenol, a naphthol or ananiline as the coupler component; azomethine dyes having a phenol, anaphthol or a hetero-cyclic ring (e.g., pyrrolotriazole) as the couplercomponent; polymethine dyes such as cyanine dye, oxonol dye andmerocyanine dye; carbonium dyes such as diphenylmethane dye,triphenylmethane dye and xanthene dye; phthalocyanine dyes;anthraquinone dyes; and indigo-thioindigo dyes.

These dyes may be a dye which provides a yellow, magenta or cyan colorfor the first time when a part of the chromophore is dissociated. Inthis case, the counter cation may be an inorganic cation such as alkalimetal and ammonium, an organic cation such as pyridinium and quaternaryammonium salt, or a polymer cation having such a cation as a partialstructure.

Examples of the black coloring material which can be used includedis-azo, tris-azo and tetra-azo dyes and a dispersion of carbon black.

[Ink Jet Recording Method]

According to the ink jet recording method of the present invention, anenergy is provided to the ink for ink jetting and thereby an image isformed on a known image-receiving material, namely, plain paper, resincoated paper, ink jet special paper described, for example, inJP-A-8-169172, JP-A-8-27693, JP-A-2-276670, JP-A-7-276789,JP-A-9-323475, JP-A-62-238783, JP-A-10-153989, JP-A-10-217473,JP-A-10-235995, JP-A-10-337947, JP-A-10-217597 and JP-A-10-337947, film,electrophotographic common paper, cloth, glass, metal, ceramic or thelike.

In forming an image, a polymer latex compound may be used in combinationfor the purpose of giving glossiness or water resistance or improvingthe weather resistance. The timing of imparting the latex compound tothe image-receiving material may be before or after imparting thecoloring agent or simultaneously with it. Accordingly, the site to whichadded may be in the image-receiving paper or ink or a liquid materialcomposed of the polymer latex alone may be prepared and used. Morespecifically, the methods described in JP-A-2002-166638,JP-A-2002-121440, JP-A-2002-154201, JP-A-2002-144696, JP-A-2002-80759,JP-A-2002-187342 and JP-A-2002-172774 can be preferably used.

The recording paper and recording film used in the ink jet printingusing the ink of the present invention are described below. The supportwhich can be used for the recording paper or film is produced, forexample, from a chemical pulp such as LBKP and NBKP, a mechanical pulpsuch as GP, PGW, RMP, TMP, CTMP, CMP and CGP, a waste paper pulp such asDIP, or the like by mixing, if desired, additives such as conventionallyknown pigment, binder, sizing agent, fixing agent, cation agent andpaper strength increasing agent and then sheeting the mixture usingvarious devices such as Fourdrinier paper machine and cylinder papermachine. Other than this support, synthetic paper or plastic film may beused. Th thickness of the support is preferably from 10 to 250 μm andthe basis weight is preferably from 10 to 250 g/m². An ink-acceptinglayer (i.e., ink-receiving layer) and a backcoat layer may be providedon the support as it is or may be provided after providing a size pressor anchor coat layer using starch, polyvinyl alcohol and the like. Thesupport may also be subjected to a flattening treatment (e.g., smoothingtreatment) by a calendering device such as machine calender, TG calenderand soft calender. In the present invention, the support is preferablypaper or plastic film of which both surfaces are laminated withpolyolefin (for example, polyethylene, polystyrene, polyethyleneterephthalate, polybutene or a copolymer thereof). In the polyolefin, awhite pigment (for example, titanium oxide or zinc oxide) or a tintingdye (for example, cobalt blue, ultramarine or neodymium oxide) ispreferably added.

The ink-accepting layer (i.e., ink-receiving layer) provided on thesupport contains a pigment and an aqueous binder. The pigment ispreferably a white pigment. The white pigment includes a white inorganicpigment such as calcium carbonate, kaolin, talc, clay, diatomaceousearth, synthetic amorphous silica, aluminum silicate, magnesiumsilicate, calcium silicate, aluminum hydroxide, alumina, lithopone,zeolite, barium sulfate, calcium sulfate, titanium dioxide, zinc sulfideand zinc carbonate, and an organic pigment such as styrene-base pigment,acryl-base pigment, urea resin and melamine resin. The white pigmentcontained in the ink-accepting layer is preferably a porous inorganicpigment, more preferably a synthetic amorphous silica having a largepore area. The synthetic amorphous silica may be either a silicic acidanhydride obtained by a dry production method or a silicic acid hydrateobtained by a wet production method but is preferably a silicic acidhydrate.

Examples of the aqueous binder contained in the ink-accepting layerinclude water-soluble polymers such as polyvinyl alcohol,silanol-modified polyvinyl alcohol, starch, cationized starch, casein,gelatin, carboxymethyl cellulose, hydroxyethyl cellulose,polyvinylpyrrolidone, polyalkylene oxide and polyalkylene oxidederivative, and water-dispersible polymers such as styrene butadienelatex and acryl emulsion. These aqueous binders can be used individuallyor in combination of two or more thereof. Among these, polyvinyl alcoholand silanol-modified polyvinyl alcohol are preferred in view ofattaching property (i.e., adhesive property) to the pigment and peelingresistance of the ink-accepting layer.

The ink-accepting layer may contain a mordant, a water-proofing agent, alight fastness enhancer, a surfactant and other additives in addition tothe pigment and the aqueous binder.

The binder added to the ink-accepting layer is preferably immobilizedand for this purpose, a polymer mordant is preferably used.

The polymer mordant is described in JP-A-48-28325, JP-A-54-74430,JP-A-54-124726, JP-A-55-22766, JP-A-55-142339, JP-A-60-23850,JP-A-60-23851, JP-A-60-23852, JP-A-60-23853, JP-A-60-57836,JP-A-60-60643, JP-A-60-118834, JP-A-60-122940, JP-A-60-122941,JP-A-60-122942, JP-A-60-235134, JP-A-1-161236 and U.S. Pat. Nos.2,484,430, 2,548,564, 3,148,061, 3,309,690, 4,115,124, 4,124,386,4,193,800, 4,273,853, 4,282,305 and 4,450,224. An image-receivingmaterial containing the polymer mordant described in JP-A-1-161236(pages 212 to 215) is particularly preferred. When the polymer mordantdescribed in this patent publication is used, an image having excellentimage quality can be obtained and at the same time, light fastness ofthe image is improved.

The water-proofing agent is effective for water-proofing the image. Thewater-proofing agent is preferably a cationic resin. Examples of thecationic resin include polyamidopolyamine epichlorohydrin,polyethyleneimine, polyaminesulfone, poly-dimethyldiallylammoniumchloride, cation polyacrylamide and colloidal silica. Among thesecationic resins, polyamidopolyamine epichlorohydrin is preferred. Thecontent of the cationic resin is preferably from 1 to 15 wt %, morepreferably from 3 to 10 wt %, based on the entire solid content of theink-accepting layer.

Examples of the light fastness enhancer include zinc sulfate, zincoxide, hindered amine-base antioxidants and benzophenone-base orbenzotriazole-base ultraviolet absorbents. Among these, zinc sulfate ispreferred.

The surfactant functions as a coating aid, a peeling property improver,a sliding property improver or an antistatic agent. The surfactant isdescribed in JP-A-62-173463 and JP-A-62-183457. In place of thesurfactant, an organic fluoro compound may be used. The organic fluorocompound is preferably hydrophobic. Examples of the organic fluorocompound include a fluorine-containing surfactant, an oily fluorine-basecompound (for example, fluorine oil) and a solid fluorine compound resin(for example, ethylene tetrafluoride resin) . The organic fluorocompound is described in JP-B-57-9053 (columns 8 to 17), JP-A-61-20994and JP-A-62-135826. Other additives added to the ink-accepting layerinclude a pigment dispersant, a thickener, a defoaming agent, a dye, afluorescent brightening agent, an antiseptic, a pH adjusting agent, amatting agent, a hardening agent and the like. The ink-accepting layermay be either one layer or two layers.

In the recording paper or film, a backcoat layer may also be provided.Examples of the component which can be added to this layer include awhite pigment, an aqueous binder and other components. Examples of thewhite pigment contained in the backcoat layer include white inorganicpigments such as precipitated calcium carbonate, heavy calciumcarbonate, kaolin, talc, calcium sulfate, barium sulfate, titaniumdioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminumsilicate, diatomaceous earth, calcium silicate, magnesium silicate,synthetic amorphous silica, colloidal silica, colloidal alumina,pseudo-boehmite, aluminum hydroxide, alumina, lithopone, zeolite,hydrolyzed halloysite, magnesium carbonate and magnesium hydroxide, andorganic pigments such as styrene-base plastic pigment, acryl-baseplastic pigment, polyethylene, microcapsule, urea resin and melamineresin.

Examples of the aqueous binder contained in the backcoat layer includewater-soluble polymers such as styrene/maleate copolymer,styrene/acrylate copolymer, polyvinyl alcohol, silanol-modifiedpolyvinyl alcohol, starch, cationized starch, casein, gelatin,carboxymethyl cellulose, hydroxyethyl cellulose andpolyvinylpyrrolidone, and water-dispersible polymers such as styrenebutadiene latex and acryl emulsion. Other components contained in thebackcoat layer include a defoaming agent, a foam inhibitor, a dye, afluorescent brightening agent, an antiseptic, a water-proofing agent andthe like.

A polymer latex may be added to a constituent layer (including thebackcoat layer) of the ink jet recording paper or film. The polymerlatex is used for the purpose of improving film properties, for example,stabilizing the dimension and preventing the curling, adhesion or filmcracking. The polymer latex is described in JP-A-62-245258,JP-A-62-1316648 and JP-A-62-110066. When a polymer latex having a lowglass transition temperature (40° C. or less) is added to a layercontaining the mordant, the layer can be prevented from cracking orcurling. Also, by adding a polymer latex having a high glass transitiontemperature to the backcoat layer, curling can be prevented.

The ink of the present invention is not limited on the ink jet recordingsystem and is used in a known system, for example, an electric chargecontrolling system of ejecting out the ink by using the electrostaticinduction force, a drop-on-demand system (pressure pulse system) ofusing an oscillation pressure of a piezo device, an acoustic ink jetsystem of converting electric signals into acoustic beams, irradiatingthe beams on the ink and ejecting out the ink using the radiationpressure, a thermal ink jet system of heating the ink to form bubblesand utilizing the generated pressure. The ink jet recording systemincludes a system of ejecting a large number of small volumes ofso-called photo-ink having a low concentration, a system designed toimprove the image quality by using a plurality of inks each havingsubstantially the same hue but a different concentration, and a systemof using colorless transparent ink.

EXAMPLES (Synthesis Example)

The synthesis method of the dye mixture of the present invention isdescribed in detail below by referring to Examples, however, the presentinvention is not limited to these Examples. In Examples, the temperatureis in the centigrade scale.

A representative dye mixture of the present invention can be derived,for example, from the following synthesis route. In the followingExamples, max means an absorption maximum wavelength and εmax means amolar absorption coefficient at the absorption maximum wavelength.

Synthesis Example 1 Synthesis of Compound A

26.0 g of 4-nitrophthalonitrile (produced by Tokyo Kasei) was dissolvedin 200 mL of DMSO (dimethylsulfoxide) in a nitrogen stream and to theobtained solution under stirring at an inner temperature of 20° C., 30.3g of sodium 3-mercapto-propane-sulfonate (produced by Aldrich) wasadded. To the resulting solution under stirring at an inner temperatureof 20° C., 24.4 g of anhydrous sodium carbonate was gradually added.Subsequently, the reaction solution was heated to 30° C. while stirringand then stirred at the same temperature for 1 hour. After cooling to20° C., the reaction solution was filtered by Nutsche, the filtrate waspoured in 15,000 mL of ethyl acetate, thereby crystallizing, and thenstirred at room temperature for 20 minutes, and the precipitated crudecrystals were filtered by Nutsche, washed with ethyl acetate and dried.The obtained crude crystals were recrystallized from methanol/ethylacetate to obtain 42.5 g of Compound A. ¹H-NMR (DMSO-d6), δ value TMSstandard: 1.9-2.0 (2H, t); 2.5-2.6 (2H, m); 3.2-3.3 (2H, t); 7.75-7.85(1H, d); 7.93-8.03 (1H, d); 8.05-8.13 (1H, s).

Synthesis Example 2 Synthesis of Compound B

42.4 g of Compound 1 was dissolved in 300 mL of acetic acid and to theobtained solution under stirring at an inner temperature of 20° C., 2.5g of Na₂WO₄·2H₂O was added. Thereafter, the solution was cooled to aninner temperature of 10° C. in ice bath. Thereto, 35 mL of aqueoushydrogen peroxide (30%) was gradually added dropwise while caring aboutheat generation. After stirring at an inner temperature of 15 to 20° C.for 30 minutes, the reaction solution was heated to an inner temperatureof 60° C. and then stirred at the same temperature for 1 hour. Aftercooling to 20° C., the reaction solution was poured in 1,500 mL of ethylacetate and then stirred at the same temperature for 30 minutes, and theprecipitated crude crystals were filtered by Nutsche, washed with 200 mLof ethyl acetate and dried. The obtained crude crystals were washedunder heat using methanol/ethyl acetate and thereby purified to obtain41.0 g of Compound B. ¹H—NMR (DMSO-d6), δ value TMS standard: 1.8-1.9(2H, t); 2.4-2.5 (2H, m); 3.6-3.7 (2H, t); 8.3-8.4 (1H, d); 8.4-8.5 (1H,d); 8.6-8.7 (1H, s).

Synthesis Example 3 Synthesis of Compound 102 of the Present Invention

In a three-neck flask with a condenser tube, 40.36 g of compound B wasdissolved in 80 mL of ethylene glycol at 80° C. in a nitrogen stream.While stirring, 4.0 g of cupric chloride (anhydride) was added and afterelevating the inner temperature to 100° C., the solution was stirred atthe same temperature for 2 hours, then cooled to an inner temperatureof. 60° C. Thereafter, 200 mL of methanol was gradually injected andthen refluxed for 30 minutes. The inner temperature was lowered to roomtemperature and the precipitate was collected by filtration and washedwith 150 mL of methanol. The obtained crude crystals were dissolved in150 mL of an aqueous 0.1N LiOH solution, insoluble matters wereseparated by filtration and after elevating the inner temperature to 60°C., 50 mL of dimethylacetamide (DMAc) was injected thereto. Whilekeeping the inner temperature at 80° C., 300 mL of ethanol was graduallyadded and then refluxed for 30 minutes. The inner temperature waslowered to room temperature and the precipitate was filtered and washedwith heated methanol. This operation (addition of ethanol to an aqueouslithium hydroxide solution of the compound, and reprecipitation) wasrepeated twice. The purification was performed by gel permeationchromatography (SEPHADEX™ LH-20, produced by Pharmacia, developingsolvent: water) to obtain 24.2 g of Compound 102. The compound wasidentified by the following method. Using mass spectrometry {LC/MS(Model TSQ-7000, LC: Model HP-1090); LC column (TSK-gelODS8OTs, 2×150mm, detection: 580(±)20 nm & MCD); eluent and flow rate (water/methanol,0.1% acetic acid/triethylamine buffer, 0.2 mL/min); LC/MS ionization;ESI-negative}, the analysis was performed from the peak of LCchromatogram and the MS spectrum. As a result, the obtained compound wasconfirmed as the objective phthalocyanine compound of the presentinvention. The counter cation M of the ionic hydrophilic group (—SO₃M)was determined by ion chromatography and atomic absorption method andfound to be M=Li/Na=9/1. λmax=628.8 nm; εmax=64,100 (in H₂O).

The present invention is described below by referring to Examples,however, the present invention is not limited by these Examples.

Example 1

<Solubility>

32.8 mg,(2.0×10⁻⁵ mol) of Phthalocyanine Compound (171) of the presentinvention was weighed and deionized water was added thereto to make 100ml. The resulting solution was stirred at 25° C. for 10 minutes toprepare a sample solution. In the same manner, a sample solution wasprepared by using methanol as the water-miscible organic solvent inplace of deionized water. Furthermore, samples solutions with adeionized aqueous solution or a methanol solution were prepared by usingan equimolar amount of a phthalocyanine compound different only in thecounter cation (counter cation: sodium ion, potassium ion or ammoniumion) from the compound of the present invention.

In the Table below, for example, 171-Na salt shown in the column ofCompound No. means that the compound is a phthalocyanine compound havingthe same structure as Compound 171 but only the counter cation ischanged to sodium. These phthalocyanine compounds having a predeterminedcounter cation were synthesized by using a raw material, intermediate orreaction agent having a predetermined counter salt in the case ofcompounds where the counter cation was lithium, sodium or potassium, andby exchanging the counter salt of the compound having a potassium saltin the case of compounds where the counter cation was ammonium. The kindand ratio of the counter cation were analyzed by ion chromatography andit was confirmed that in each compound, 90% or more of the countercation was the predetermined counter cation.

The dissolution degree of each sample solution was determined by thefollowing three methods: (1) the presence or absence of undissolvedmatters was judged with an eye, (2) after filtering through amicrofilter having an average pore size of 0.25 μm, the presence orabsence of undissolved matters on the filter was confirmed, and (3) thesolution was filtered and measured on the absorption spectrum and whenthe absorbance obtained was only 90% or less of the absorbancecalculated from the molar absorption coefficient, it was judged thatinsoluble matters were present in the sample solution. Sample solutionsjudged to have complete dissolution in all tests were rated ◯, andsample solutions judged to have undissolved matters in any one test wererated ×. The results are shown in Table.

<Spectral Absorption Property>

A 2 wt % aqueous solution of the phthalocyanine compound of the presentinvention was further 1,000-fold diluted with distilled water and theobtained solution was analyzed by a spectrophotometer under thefollowing measurement conditions. The absorbance ratio b/a determinedfrom the spectral absorption curve of the phthalocyanine compound usedin Example is shown in Table below.

(Measuring Conditions)

Device used: Shimadzu Auto-Recording Spectro-photometer UV-260, cell:quartz cell, light path length: 10 mm, measuring temperature: 20° C.,diluting solution: distilled water (pH: 7.0). TABLE 21 Solvent CounterDeionized b/a Compound No. Cation Water Methanol Value 171 Li ◯ ◯ 0.62Invention 171-Na salt Na ◯ X 0.64 Comparison 171-K salt K ◯ X 0.63Comparison 171-NH₄ salt NH₄ ◯ X 0.54 Comparison

In phthalocyanine compounds having a spectral absorption curvesatisfying the requirement specified in the present invention, thesolubility in water is sufficiently high whichever counter cation thecompound has. However, in methanol, only a phthalocyanine compoundhaving lithium ion as the counter cation is dissolved. It is seen fromthis that in phthalocyanine compounds having the same structure, thesolubility in a water-miscible organic solvent can be greatly improvedonly by changing the counter cation. It is also seen that even when thecounter cation is changed, the spectral absorption property specified inthe present invention is not greatly changed

Example 2

Deionized water was added to the following components to make 1 literand the resulting solution was stirred for 1 hour under heating at 30 to40° C. Thereafter, the solution was adjusted to a pH of 9 with 10 mol/Lof KOH and then filtered under pressure through a microfilter having anaverage pore size of 0.25 μm to prepare an ink solution for cyan color.Composition of Ink Solution A: Dye of the Present Invention (102)  6.80g Diethylene glycol 10.65 g Glycerin 14.70 g Diethylene glycol monobutylether 12.70 g Triethanolamine  0.65 g Olefin E1010  0.9 g

Ink Solutions B and C were prepared in the same manner as Ink Solution Aexcept for changing the phthalocyanine compound as shown in Table below.As the ink solution for comparison, Comparative Ink Solutions 1 to 3were prepared using phthalocyanine compounds where only the countercation was changed as shown in the Table. Also, Comparative Ink Solution4 was prepared by changing the phthalocyanine compound to aphthalocyanine compound (sodium salt) having a spectral absorption curvenot satisfying the requirement specified in the present invention. Inthe Table, for example, 171-Na salt shown in the column of Compound No.means that the compound is a phthalocyanine compound having the samestructure as Compound 171 and only the counter cation is changed tosodium.

When the dye was changed, a dye was used such that the amount addedthereof became equimolar to Ink Solution A.

(Recording and Evaluation of Image)

Each ink for ink jetting of Examples (Ink Solutions A to C) andComparative Examples (Comparative Ink Solutions 1 to 4) was subjected tothe following evaluations. The results obtained are shown in Table 22.In the Table, “color tone”, “paper dependency”, “water resistance” and“light fastness” were evaluated after an image was recorded using eachink for ink jetting on a photo gloss paper (PM Photographic Paper“KOTAKU” (KA420PSK, EPSON), produced by EPSON) in an ink jet printer(PM-700C, manufactured by EPSON).

<Color Tone>

The image formed on the photo gloss paper was subjected to colorimetryof the reflection spectrum at intervals of 10 nm in the region from 390to 730 nm and a* and b* were calculated based on the CIE (InternationalCommission on Illumination) L*a*b* color space system.

By comparing with the standard cyan color sample (a color when solidbatches of proof provided from 21 companies as members of the JapanPrinting Machinery Manufacturers Association were subjected tocolorimetry and the printing was performed using Japan Color Ink SF-90and Japan Paper to give a smallest color difference (ΔE) from theaverage value) of JAPAN Color of JNC (Japan Printing MachineryManufacturers Association), the preferred cyan color tone was defined asfollows:

L*: in the range of 53.6±0.2,

◯: a* (in the range of −35.9±6) and b* (in the range of −50.4±6)

Δ: only one of a* and b* (in the preferred region defined in ◯ above)

×: neither a* nor b* (both out of the preferred region defined in ◯above)

The colorimetry values of the standard cyan color sample of JAPAN colorused as the reference are shown below: L*:   53.6 ± 0.2 a*: −37.4 ± 0.2b*: −50.2 ± 0.2 ΔE: 0.4 (0.1 to 0.7)(1) Printer:

MANLORAND R-704, ink: JAPAN Color SF-90, paper: TOKUHISHI ART.

(2) Colorimetry:

Colorimeter: X-rite 938, 0/45, D50, 2 deg., black backing.

<Paper Dependency>

The image formed on the above-described photo gloss paper and the imageseparately formed on PPC plain paper were compared on the color tone.The evaluation was performed by the two-stage rating, that is, A (good)is when the difference between two images is small, and B (bad) is whenthe difference between two images is large.

<Water Resistance>

The photo gloss paper having formed thereon an image was dried at roomtemperature for 1 hour, dipped in deionized water for 10 seconds andthen naturally dried at room temperature. The blurring was observed andevaluated by the three-stage rating, that is, A is no blurring, B isslight blurring and C is serious blurring.

<Light Fastness>

On the photo gloss paper having formed thereon an image, xenon light(85,000 1×) was irradiated for 7 days using a weather meter (AtlasWeather-o-meter C. I65, manufactured by Atlas (Illinois, U.S.A.)). Theimage density before and after the xenon irradiation was measured by areflection densitometer (X-Rite 310TR) and evaluated as the dye residualpercentage. The reflection density was measured at three points of 1,1.5 and 2.0. The dye residual percentage was evaluated by thethree-stage rating, that is, A is 70% or more at any density, B is lessthan 70% at one or two points, and C is less than 70% at all densities.

<Dark Heat Storability>

The photo gloss paper having formed thereon an image was stored for 7days under the conditions of 80° C. and 15% RH. The image density beforeand after the storage was measured by a reflection densitometer (X-Rite310TR) and evaluated as the dye residual percentage. The dye residualpercentage was evaluated at three points having a reflection density of1, 1.5 and 2.0. A is a dye residual percentage of 90% or more at anydensity, B is less than 90% at two points, and C is less than 90% at alldensities.

<Ozone Gas Resistance>

In a box set to an ozone gas concentration of 0.5±0.1 ppm, roomtemperature and dark place using a Siemens-type ozonizer to which ana.c. voltage of 5 kV was applied while passing a dry air through thedouble glass tube, the photo gloss paper having formed thereon an imagewas left standing for 7 days. The image density before and afterstanding in an ozone gas atmosphere was measured by a reflectiondensitometer (X-Rite 310TR) and evaluated as the dye residualpercentage. The reflection density was measured at three points of 1,1.5 and 2.0. The ozone gas concentration in the box was set using anozone gas monitor (Model OZG-EM-01) manufactured by APPLICS. Theevaluation was performed by the three-stage rating, namely, A is a dyeresidual percentage of 70% or more at any density, B is less than 70% atone or two points, and C is less than 70% at all densities.

<Spectral Absorption Property>

The absorbance ratio b/a determined from the spectral absorption curveof phthalocyanine compound in the same manner as in the method ofExample 1 is shown.

<Bronze Phenomenon>

The photo gloss paper having formed thereon an image was dried for 24hours and then the presence or absence of generation of bronzephenomenon was observed with an eye and evaluated. A sample where thebronze phenomenon was not confirmed at all is rated ◯, and a samplewhere the generation of bronze phenomenon was confirmed is rated X.Here, when a bronze phenomenon is generated, the printing densitybecomes lower than the case having no generation of a bronze phenomenon.Therefore, the generation of bronze phenomenon can also be confirmed bythe decrease of printing density. TABLE 22 Water Ozone Bronze InkCompound Counter Color Paper Resist- Light Dark Heat Resist- b/a Pheno-Solution No. Cation Tone Dependency ance Fastness Storability ance Valuemenon A 171 Li ◯ A A A A A 0.62 ◯ B 102 Li ◯ A A A A A 0.74 ◯ C 172 Li ◯A A A A A 0.67 ◯ Comparative 171-Na Na ◯ A A A A A 0.64 X Example 1 saltComparative 171-K K ◯ A A A A A 0.63 X Example 2 salt Comparative171-NH₄ NH₄ ◯ A A A A A 0.54 X Example 3 salt Comparative Compara- Na ΔB B B A C 1.00 ◯ Example 4 tive Compound 1

It is seen from the Table above that when a phthalocyanine compoundhaving a specific spectral absorption curve and a specific structure isused, an ink for ink jetting having excellent (color) hue and smallpaper dependency and being excellent in the water resistance, lightfastness and ozone resistance can be obtained and also that when thecounter ion for the ionic hydrophilic group is not lithium ion, a bronzephenomenon is generated.

Furthermore, it is seen that in the case of a phthalocyanine compoundhaving a spectral absorption curve out of the specified range of thepresent invention and not strongly forming the aggregated state, the(color) hue and fastness are very bad, though a bronze phenomenon is notgenerated even if the counter cation is sodium ion.

Example 3

Using the same cartridge as produced in Example 2, an image was printedon Ink Jet Paper Photo Gloss Paper EX produced by Fuji Photo Film Co.,Ltd. by means of the same printer as used in Example 2, and evaluated inthe same manner as in Example 2. Then, the same results as in Example 2were obtained.

Example 4

The same ink as produced in Example 2 was filled in a cartridge of InkJet Printer BJ-F850 (manufactured by CANON) and using this printer, animage was printed on a photo gloss paper GP-301 produced by the samecompany and evaluated in the same manner as in Example 2. Then, the sameresults as in Example 2 were obtained.

Example 5

A test was performed by using the same operation as in Example 2 exceptthat the test method of Example 2 was changed to the followingenvironmental test method. That is, an oxidative gas resistance testmethod simulating the outdoor environment exposed to oxidative gasessuch as exhaust gas of automobile and irradiation with solar light wasperformed according to an oxidation resistance test method using afluorescent light irradiation chamber at a relative humidity of 80% anda hydrogen peroxide concentration of 120 ppm described in H. Iwano etal., Journal of Imaging Science and Technology, Vol. 38, 140-142 (1944).The test results were the same as those in Example 2.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

This application is based on Japanese patent application No. 2002-12864filed on Jan. 22, 2002, the entire contents thereof being herebyincorporated by reference.

Industrial Applicability:

Phthalocyanine-base dyes widely used in general at present, representedby Direct Blue 87 and Direct Blue 199, are excellent in the lightfastness as compared with generally known magenta dyes, yellow dyes andtriphenylmethane-base cyanine dyes.

However, the phthalocyanine-base dyes provide a greenish (color) hueunder acidic conditions and are improper for a cyan ink. In the case ofusing these dyes for a cyanine ink, these are most suitably used underconditions from neutral to alkaline. However, even if the ink is in theregion from neutral to alkaline, when the material on which an image orthe like is recorded is an acidic paper, the (color) hue of the printedmatter may greatly change.

Furthermore, discoloration to a greenish (color) hue or decolorationoccurs due to oxidative gases such as nitrogen oxide gas and ozone,which are often taken as a problem also from an environmental issue, andthis simultaneously causes reduction in the printing density.

On the other hand, triphenylmethane-base dyes provide a good (color) huebut are very inferior in the light fastness, resistance against ozonegas and the like.

In view of the above problems, the following effects have been found outby the present invention.

According to the present invention, 1) an ink comprising aphthalocyanine compound, having absorption properties with excellentcolor reproducibility and showing sufficiently high fastness to light,heat, humidity and active gases in the environment, 2) an inkcomposition for printing such as ink jetting, using the above-describedink and capable of forming an image free of generation of a bronzephenomenon, and 3) a method capable of improving the fastness of theimage recorded material against light and active gases in theenvironment, particularly ozone gas, can be provided.

1. An ink comprising a water-soluble phthalocyanine compound, wherein inthe spectral absorption curve of an aqueous solution of saidphthalocyanine compound, the absorbance ratio b/a of the maximumabsorbance b in the absorption band of 660 to 680 nm and the maximumabsorbance a in the absorption band of 600 to 640 nm is less than 0.8and the counter ion for the ionic hydrophilic group of saidphthalocyanine compound is lithium ion.
 2. An ink comprising awater-soluble phthalocyanine compound, wherein said phthalocyaninecompound is represented by the following formula (I): Formula (I):

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ each independently representsa hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, analkenyl group, an aralkyl group, an aryl group, a heterocyclic group, acyano group, a hydroxyl group, a nitro group, an amino group, analkylamino group, an alkoxy group, an aryloxy group, an amido group, anarylamino group, a ureido group, a sulfamoylamino group, an alkylthiogroup, an arylthio group, an alkoxycarbonylamino group, a sulfonamidogroup, a carbamoyl group, a sulfamoyl group, a sulfonyl group, analkoxycarbonyl group, a heterocyclic oxy group, an azo group, an acyloxygroup, a carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group,an aryloxycarbonylamino group, an imido group, a heterocyclic thiogroup, a sulfinyl group, a phosphoryl group or an acyl group and eachmay further have a substituent; W₁, W₂, W₃ and W₄ each independentlyrepresents the group represented by R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈, asulfonylsulfamoyl group or an acylsulfamoyl group and each may furtherhave a substituent, provided that at least one of W₁, W₂, W₃ and W₄ isan ionic hydrophilic group by itself or has an ionic hydrophilic groupas a substituent, provided that the counter ion for the ionichydrophilic group is lithium ion; l, m, n and p each represents aninteger of 1 or 2; and M represents a hydrogen atom, a metal element, ametal oxide, a metal hydroxide or a metal halide.
 3. The ink as claimedin claim 2, wherein said formula (I) is represented by the followingformula (II):

wherein Z₁, Z₂, Z₃ and Z₄ each independently represents a substituted orunsubstituted alkyl group, a substituted or unsubstituted cycloalkylgroup, a substituted or unsubstituted alkenyl group, a substituted orunsubstituted aralkyl group, a substituted or unsubstituted aryl groupor a substituted or unsubstituted heterocyclic group, q₁, q₂, q₃ and q₄each independently represents an integer of 1 or 2, a₃₁, a₃₂, a₃₃ anda₃₄ each independently represents an integer of 1 or 2, M has the samemeaning as M in formula (I), and at least one of Z₁, Z₂, Z₃ and Z₄ hasan ionic hydrophilic group as a substituent, provided that the counterion for the ionic hydrophilic group is lithium ion.
 4. The ink asclaimed in claim 2, wherein said formula (I) is represented by thefollowing formula (IlI):

wherein R₂₁, R₂₂, R₂₃ and R₂₄ each independently represents a hydrogenatom, a substituted or unsubstituted alkyl group, a substituted orunsubstituted cycloalkyl group, a substituted or unsubstituted alkenylgroup, a substituted or unsubstituted aralkyl group, a substituted orunsubstituted aryl group or a substituted or unsubstituted heterocyclicgroup, V₁₁, V₁₂, V₁₃ and V₁₄ each independently represents a substitutedor unsubstituted alkyl group, a substituted or unsubstituted cycloalkylgroup, a substituted or unsubstituted alkenyl group, a substituted orunsubstituted aralkyl group, a substituted or unsubstituted aryl group,or a substituted or unsubstituted heterocyclic group, M has the samemeaning as M in formula (I), and at least one of R₂₁, R₂₂, R₂₃, R₂₄,V₁₁, V₁₂, V₁₃ and V₁₄ has an ionic hydrophilic group as a substituent,provided that the counter ion for the ionic hydrophilic group is lithiumion.
 5. The ink as claimed in claim 3, wherein in formula (II),q₁=q₂=q₃=q₄=2.
 6. An ink for ink jetting, comprising the ink claimed inclaim
 1. 7. An ink jet recording method comprising forming an image onan image-receiving material using the ink for ink jetting claimed inclaim 6, the image receiving material comprising a support havingthereon an ink image-receiving layer containing a white inorganicpigment particle.
 8. A method for improving ozone gas discoloration ofan image recorded material, comprising forming an image using the inkclaimed in claim
 1. 9. A water-soluble phthalocyanine compoundrepresented by the following formula (IV):

wherein Z₁, Z₂, Z₃ and Z₄ each independently represents a substituted orunsubstituted alkyl group, a substituted or unsubstituted cycloalkylgroup, a substituted or unsubstituted alkenyl group, a substituted orunsubstituted aralkyl group, a substituted or unsubstituted aryl groupor a substituted or unsubstituted heterocyclic group, q₁, q₂, q₃ and q₄each independently represents an integer of 1 or 2, a₃₁, a₃₂, a₃₃ anda₃₄ each independently represents an integer of 1 or 2, M has the samemeaning as M in formula (I), and at least one of Z₁, Z₂, Z₃ and Z₄ hasan ionic hydrophilic group as a substituent, provided that the counterion for the ionic hydrophilic group is lithium.